Specification
DESCRIPTION DEVELOPING SOLUTION ANDMETHOD FOR PRODUCTION OF FINELY PATTERNED
MATERIAL
Technical Field
The present invention relates to a developing solution, and a method for producing a finely patterned material using the same. More particularly, the invention relates to a developing solution used in the development of thermosensitive inorganic resists, which utilizes an oxidation/reduction reaction of transition metal oxides or phase transfer.
Background Art
As a means for realizing shape patterns of controlled angles withhighresolution, therehavebeenproposedmethods ofutilizing inorganic resists. These have been reported to include methods of using, as an active energy source for drawing shape patterns, an electron beam or an ion beam (see, for example, Japanese Patent ApplicationLaid-Open (JP-A) No. 6-132188, andJP-ANo. 8-69960), methods of using far ultraviolet radiation (see, for example, JP-A No. 2004-172272), methods of using laser radiation (see, for example, Japanese Journal of Applied Physics, 44, 3574-3577, 2005), and the like.
Among the methods making use of laser radiation as the drawing energy, a method of using a metal oxide as the material for inorganic resist has been proposed (see, for example, JP-A No. 2003-315988 and JP-ANo. 2004-152465) . Since this inorganic
resist leads to the formation of latent images through thermosensitive reactions, it is possible to achieve exposure of a pattern smaller than the spot diameter, even through exposure to a visible laser light at about 405 nm. For this reason, the method has been paid attention as a technology which is useful for the optical disk mastering technology in coping with Blu-ray Disc (registeredtrademark) orevenfurtherincreasesinrecording density.
Here, the developing solution used in the resist development will be described. In addition to the development of photographic films, the development of the organic resists which are used in the production of semiconductors or plate making, is carried out by means of alkaline aqueous solutions mixed with various additives. These developing solutions undergo deterioration as a result of the consumption of alkali sources due to chemical reactions with developing products, as well as the reaction with carbon dioxide in air, or the like. When a developing solution which has been worn out and thus has the alkali source consumed up, is to be replaced with a new developing solution, if all of the developing solution is completely exchanged, development properties such as the rate of development or the contrast may be changed to a large extent in some cases . As amethod of avoiding this, amethod of discarding only a half of the worn out developing solution, and replenishing the remaining portion with a new developing solution, or a method of adding an alkali source at a high concentration to the worn out developing solution, to thereby supplement the consumed portion, is generally known.
Furthermore, a method of replacing all of the developing solution, subsequently repeating preliminary development until the development properties are stabilized, and using a developing solution which has been stored for a while, is also adopted.
The rate of development is largely affected by the pH of the developing solution, and in general, the rate of development is increased as the pH value is increased (as the alkalinity becomes stronger). In the case of developing black-and-white photographs, the pH of the developing solution is adjusted to control the reducing power of metol (N-methyl-p-aminophenol hemisulfate), hydroquinone, phenidone
(l-phenyl-3-pyrazolidone) or the like, which are the main developing agents, and as the alkali is stronger, the reducing power of the main developing agent becomes stronger. It is known that when a buffering agent such as borax (sodium tetraborate) , sodiummetaborate, or sodium carbonate is mixed into a developing solution, the pH value is stabilized, and at the same time, dissociation of the main developing agent is proceeded to activate the developing solution, thereby a development accelerating effect being brought about. On the other hand, when potassium bromide is incorporated in, the reaction is suppressed, the rate of development is decreased, and at the same time, development of weakly exposed parts is suppressed so that an effect of preventing "fogging" is obtained.
In regard to organic resists which are used in the production of semiconductors and the like, for example, in the case of the positive type, a latent image is f ormedby irradiating the polymer
resist with ultraviolet radiation, an electron beam or the like to cleave the polymer chain, or by generating an acidic functional group such as -COOH or -OH in the polymer chain, the latent image isneutralizedanddissolvedwithanalkalinedevelopingsolution, and thereby image formation is achieved. In the case of the negative type, image formation is achieved by making use of the difference in the solubility in an alkaline or acidic developing solution between the part where the monomer or oligomer has been polymerized by the irradiation with ultraviolet radiation or the like, and the part where no polymerization has occurred. These organic resists are such that detachment may occur prior to dissolution of the resist at excessively high pH values, while the dissolution rate may be slowed down at excessively low pH values. For this reason, a method of incorporating a buffering agent is used in order to stabilize the developing solution to an appropriate pH value. As for the type of the buffering agent, a method of employing phosphates (see, for example, JP-A No. 2005-300694), a method of employing silicates (see, for example, JP-A No. 2005-049542), a method of employing carbonates (see, for example, US Patent No. 5853963 and JP-A No. 02-002572), a method of employing carbon dioxide gas (see, for example, JP-A No. 2001-228628), and the like have been published.
An alkaline developing solution absorbs carbon dioxide gaswhencontactedwithair,andthusalkali componentsareconsumed (carbon dioxide fatigue). To prevent this, a method of incorporating a carbonate or a hydrogen carbonate into the developing solution as an alkali component or an additive, is
adopted (see, for example, JP-A No. 2002-202616).
In regard to the plat emaking of photosensitive lithographic printing plates, there has been disclosed a method of performing the plate making by applying an organic resist on a support made of aluminum. It is reported that aqueous solutions of silicates are effective as the developing solution (see, for example, JP-A No.52-127338,JP-ANo.54-062004,andJapanesePatentApplication Publication (JP-B) No. 57-007427) . This is said to be because when the aluminum support is exposed by dissolving and removing the resist by developing, it is difficult for the developing solution to corrode the support, and ad j ustment of the development properties is possible to a certain degree by adjusting the ratio and concentrations of metal oxide and silicon oxide, which is a silicate component. Furthermore, silicates are reported to exhibit notable effects in view of preventing contamination by hydrophili zing the intaglio-shaped exposed parts of the support, which are the parts to be developed (see, for example, JP-A No. 08-160633, JP-ANo. 11-065129, JP-ANo. 2003-015318, JP-ANo. 2003-035960, JP-A No. 2003-043701, JP-A No. 2003-043702, JP-A No. 2003-057847, JP-A No. 2003-057848, JP-A No. 2003-057849, JP-A No. 2003-107743, JP-A No. 2003-270775, and JP-A No. 2003-270776).
Inadditiontothis, asamethodofshorteningthedevelopment time, there may be mentioned a method of imparting the developing solution with the affinity to polymer resist. Specifically, measures such as enhancing the wettability of the resist surface by adding surfactants to the developing solution, or enhancing
the resist penetrability of the developing solution by adding an organic solvent, are being adopted.
Disclosure of the Invention
For the master stamper used in the production of optical disks, typically, a pattern is formed by applying an organic resist on a glass substrate, forming a spiral latent image with laser radiation or the like, and developing the latent image. In this case, commercially available developing apparatuses are usually operated such that a low-power laser light is irradiated from the rear surface of the glass substrate, to thus transmit through the substrate, and the transmitted laser light undergoes scattering at the surface irregularities of the organic resist, which appear along with the progress of development. Furthermore, the time point at which the ratio of the first-order scattered light to the zero-order unscattered, transmitted light reaches a value established in advance, is taken as the end point.
On the other hand, inorganic resists are often opaque to visible light, and there may occur situations where this method cannot be applied. For this reason, the development of inorganic resists frequently adopts a method of measuring in advance the time taken to reach an appropriate state of development for every type of resist master, and managing the development based on the development time. Here, when a worn-out, deteriorated developing solution is completely changed with a new one, it mayhappenthattheoptimaldevelopmenttimeorthe shapeobtainable by the development is altered to a large extent. Particularly,
in the case where the development time is changed to a large extent, the management value for the end point must be re-established, and when the developing solution composition is changed concomitantly with the development of the resist, it becomes necessary to re-establish the management value from occasion to occasion, in accordance with the change. It is known that developing solutions have the development properties gradually stabilized while they are being used for some time, and thus, under general situations of resist development, amethod of repeatingpreliminary development, and then putting the resist into actual use, is frequently used. However, in the case of master stamper for optical disks, since the resist film thickness is extremely thin to the order of nanometers, a large number of the preliminary development process will be required until the developing solution becomes stabilized by the development of resist.
Therefore, an object of this invention is to provide a developing solution which can maintain the rate of development almost constantly from the state of being fresh to the state ofbeingwornout, andatthe same time, can shortenthe development time, and a method for producing a finely patterned material using the same.
The present invention is an invention obtained as a result of devoted investigation carried out in order to solve the above-described problems of the prior art. Hereinafter, the gist of the invention will be described. First, attention was paid to the point that the rate at which an alkaline aqueous
solution used as a developing solution dissolves a metal oxide, which is the dissoluble component of an inorganic resist, is highlyacceleratedbythe salts includedinthedevelopingsolution in addition to the alkali source. Then, the relations between the type of the salts and the development properties such as the rate of development or the surface morphology, were investigated, and thus the present invention was completed. If a compound which directly exerts action to WO3, M0O3 andthelike,whicharethedissolublecomponents(acidcomponents) inthe inorganicresist, is incorporatedintoadevelopingsolution in the state of being dissolved in an alkaline aqueous solution, the rate of development is rapidly increased proportionally to the amount of incorporation, until a certain amount of incorporation is reached, and then the rate of development is slowly converged to a certain rate of development. This converged value varies depending on the type of the salts added. By incorporating these salts individually alone or as mixtures, it has become possible to shorten the time required in development, as well as to control the development time. Thereby, it has become possible to make the developing solution to maintain the rate of development almost constantly, from the state of being fresh to the state of being worn out. Here, in the case where the compound to be added is a salt, the alkali moiety may be identicalwithordifferentfromthealkali sourceofthedeveloping solution. On the other hand, when a compound having reactivity with the alkali source, for example, a basic compound weaker than the alkali source, an acidic oxide, an amphoteric oxide,
an amphoteric hydroxide or the like, is added to an alkaline aqueous solution, the compound reacts with the alkali source of the developing solution while being dissolved. As a result, an effect equivalent to the case where the alkali moiety of the salt is the same as the alkali source contained in the developing solution, can be obtained.
A first invention of the present invention is a developing solution characterized by containing:
an alkaline aqueous solution; and
at least one anion among a silicate ion, a carbonate ion, a borate ion and a phosphate ion.
A second invention of the present invention is a developing solutioncontaininganalkalineaqueous solutionandadevelopment accelerating agent, wherein the development accelerating agent is at least one among a silicate, a carbonate, a borate and a phosphate.
A third invention of the present invention is a method for producing a finely patterned material, the method including:
exposing an inorganic resist layer provided on a base material; and
developing the exposed inorganic resist with a developing solution,
wherein the developing solution contains:
an alkaline aqueous solution; and
at least one anion among a silicate ion, a carbonate ion, a borate ion and a phosphate ion.
In the first and third inventions, the alkaline aqueous
solution is preferably an aqueous solution of tetraalkylammonium hydroxide . The developing solution preferably further contains at least one among ammonium ion and an organic ammonium ion as a cation, or further contains an alkali metal ion as a cation, or further contains at least one among ammonium ion and an organic ammonium ion, and an alkali metal ion as cations.
In the first and third inventions, when the inorganic resist is developed, the anion repeatedly exerts action on the inorganic resist in the alkaline aqueous solution. Furthermore, when the inorganic resist is developed, the anion forms a bond with the inorganic resists.
In the first and third inventions, when titration is performed with an acid to determine a titration curve showing the relationship between the amount of dropwise addition and the pH, typically, the point of neutralization of the alkaline aqueous solution and an inflection point originating from the anion appear on the titration curve. It is preferable that the pH of the alkaline aqueous solution be set at a higher value compared to any of the pH of the point of neutralization and the inflection point appearing on the titration curve. Furthermore, it is preferable, in the case where titration is performed with an acid to determine a titration curve showing the relationship between the amount of dropwise addition and conductivity, that the titration curve have a minimum region between the point of neutralization of the alkaline aqueous solution and the inflection point originating from the anion.
In the second invention, the salt is preferably a product
produced by the reaction between the alkaline aqueous solution and at least one among silicon, a silicon compound, a carbon compound, a boron compound and a phosphorus compound. Furthermore, the salt is preferably a product produced by the reaction between at least one selected from the group consisting of an alkali metal compound, an ammonium compound and a basic oxide, as an alkali component, and at least one selected from the group consisting of a protonic acid, an acidic oxide, an amphotericoxideandanamphoterichydroxide, asanacidcomponent.
In the second invention, the cation of the alkali source of the alkaline aqueous solution and the cation of the development accelerating agent are preferably the same species, and in particular, it is preferable that the cation of the alkali source of the alkaline aqueous solution and the cation of the development accelerating agent be ammonium ion or an organic ammonium ion.
In the third invention, it is preferable that the method further includes a process of producing a developing solution by adding a silicate, a carbonate, a borate and a phosphate to the alkaline aqueous solution, prior to the process of exposing. Asdiscussedintheabove, accordingtothepresent invention, the rate of development can be maintained almost constantly, from the state of being fresh to the state of being worn out, and at the same time, the development time can be shortened.
Brief Description of the Drawings
Fig. 1A to Fig. 1C are schematic diagrams for explaining the reaction mechanism of an inorganic resist;
Fig. 2 is a schematic diagram for explaining the development mechanism of an inorganic resist;
Fig. 3 is a graph for explaining the relationship between the amount of dropwise addition of hydrochloric acid and the pH in the titration of a developing solution;
Fig. 4A to Fig. 4C are schematic cross-sectional views for explaining the method for producing a resist master according to an embodiment of the present invention;
Fig. 5A to Fig. 5C are schematic cross-sectional views for explaining the method for producing a resist master according to an embodiment of the present invention;
Fig. 6AtoFig. 6C are AFM diagrams for the inorganic resist master according to Comparative Example 1;
Fig. 7 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid, and the pH as well as conductivity in Comparative Example 1;
Fig. 8AtoFig. 8C are AFM diagrams for the inorganic resist master according to Comparative Example 2;
Fig. 9 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Comparative Example 2;
Fig. 10A to Fig. IOC are AFM diagrams for the inorganic resist master according to Comparative Example 3;
Fig. 11 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Comparative Example 3;
Fig. 12A to Fig. 12C are AFM diagrams for the inorganic
resist master according to Comparative Example 4;
Fig. 13 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Comparative Example 4;
Fig. 14A to Fig. 14C are AFM diagrams for the inorganic resist master according to Comparative Example 5;
Fig. 15 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Comparative Example 5;
Fig. 16A to Fig. 16C are AFM diagrams for the inorganic resist master according to Example 1;
Fig. 17 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 1;
Fig. 18 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 2;
Fig. 19 is a partial magnified view of Fig. 18;
Fig. 20 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 3;
Fig. 21 is a partial magnified view of Fig. 20;
Fig. 22A to Fig. 22C are AFM diagrams for the inorganic resist master according to Example 4;
Fig. 23 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 4;
Fig. 24 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in the case of using the developing solution saturated with additives in Example 4;
Fig. 25A to Fig. 25C are AFM diagrams for the inorganic resist master according to Example 5/
Fig. 26 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 5;
Fig. 27 is a graph showing the relationship between the amount of incorporation of a development accelerating agent and the development time in Example 6;
Fig. 28A to Fig. 28C are AFM diagrams for the inorganic resist master according to Example 7;
Fig. 29 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 7;
Fig. 30A to Fig. 30C are AFM diagrams for the inorganic resist master according to Example 8;
Fig. 31 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 8;
Fig. 32A to Fig. 32C are AFM diagrams for the inorganic resist master according to Example 9;
Fig. 33 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 9;
Fig. 34A to Fig. 34C are AFM diagrams for the inorganic resist master according to Example 10;
Fig. 35 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 10;
Fig. 36A to Fig. 36C are AFM diagrams for the inorganic resist master according to Example 11;
Fig. 37 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 11;
Fig. 38A to Fig. 38C are AFM diagrams for the inorganic resist master according to Example 12;
Fig. 39 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 12;
Fig. 40A to Fig. 40C are AFM diagrams for the inorganic resist master according to Example 13;
Fig. 41 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 13;
Fig. 42A to Fig. 42C are AFM diagrams for the inorganic resist master according to Example 14;
Fig. 43 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 14;
Fig. 44A to Fig. 44C are AFM diagrams for the inorganic resist master according to Example 15;
Fig. 45 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 15;
Fig. 4 6A to Fig. 4 6C are AFM diagrams for the inorganic resist master according to Example 16;
Fig. 47 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 16;
Fig. 48 is a graph showing the relationship between the amount of incorporation of a development accelerating agent and the development time in Example 17 to Example 20;
Fig. 49 is a graph showing the relationship between the amount of incorporation of a development accelerating agent and the development time in Example 21 to Example 24;
Fig. 50 is a graph showing the relationship between the amount of incorporation of a development accelerating agent and the development time in Example 25 and Example 2 6;
Fig. 51A to Fig. 51C are AFM diagrams for the inorganic resist master according to Example 27;
Fig. 52 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 27;
Fig. 53A to Fig. 53C are AFM diagrams for the inorganic resist master according to Example 28;
Fig. 54 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 28;
Fig. 55A to Fig. 55C are AFM diagrams for the inorganic resist master according to Example 29;
Fig. 56 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 2 9;
Fig. 57A to Fig. 57C are AFM diagrams for the inorganic resist master according to Example 30;
Fig. 58 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 30;
Fig. 5 9A to Fig. 5 9C are AFM diagrams for the inorganic resist master according to Example 31;
Fig. 60 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 31;
Fig. 61A to Fig. 61C are AFM diagrams for the inorganic resist master according to Example 32;
Fig. 62 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 32;
Fig. 63A to Fig. 63C are AFM diagrams for the inorganic resist master according to Example 33;
Fig. 64 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 33;
Fig. 65A to Fig. 65C are AFM diagrams for the inorganic resist master according to Example 34;
Fig. 66 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 34;
Fig. 67A to Fig. 67C are AFM diagrams for the inorganic resist master according to Example 35;
Fig. 68 is a graph showing the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity in Example 35;
Fig. 69 is a graph showing the relationship between the amount of incorporation of a development accelerating agent and the development time in Example 36 to Example 38; and
Fig. 70 is a graph showing the relationship between the amount of incorporation of a development accelerating agent and the development time in Example 39 to Example 42.
Best Mode for carrying out the Invention
Embodiments of the present invention will be described in the following order.
(1) First embodiment
(1-1) Inorganic resist
(1-2) Developing solution
(1-3) Reaction mechanism of inorganic resist (1-4) Reaction between inorganic resist and developing solution
(1-5) Method for producing resist master
(1-6) Method for monitoring developing solution
(2) Second embodiment
(2-1) Developing solution
(2-2) Reaction between inorganic resist and developing solution
(3) Third embodiment
(3-1) Developing solution
(3-2) Reaction between inorganic resist and developing solution
(1) First embodiment
(1-1) Inorganic resist
First, the inorganic resist used in the first embodiment of the present invention will be described.
In photolithography, inorganic resists are known to have high thermal stability compared to organic resists, and markedly highypropertyiseasilyobtainedtherewith. Forexample,organic resistssuchaspolystyrene(PS),polymethylmethacrylate(PMMA) , polyglycidyl methacrylate-chlorostyrene copolymer (GMC), poly (butene-1-sulfone) (PBS), and phenyl formaldehyde novolac, typically can only give ay property of 3 or less after development, in the case of using ultraviolet radiation, as well as even in the case of using a finely converged electron beam, ion beam or the like. In addition, y = l/(log 81 - log 80) (wherein 80: the minimum amount of exposure required for photosensitizing the resist, and 81: the amount of exposure required to completely photosensitize the resist). This is because, since organic resists have large molecular weights, the boundaries between the exposed parts and the unexposed parts become indefinite. On the other hand, inorganic resists which are made of chalcogenide
glass, a metal oxide or the like, can give a y property of greater than4, and sometimes aypropertywhichwouldexceed8 . Therefore, the inorganic resists allow steeper taper angles to be obtained, as compared to the organic resists.
In regard to the metal oxide, any material can be used
in accordance with the process for producing a desired shape
on the basematerial. As for specif ic examples thereof, titanium
monoxide(TiO),titaniumdioxide (TiO2) , bariumtitanate(BaTiO3) ,
tungstentrioxide (WO3) , tungstendioxide(WO2) , tungstenmonoxide
(WO), molybdenum trioxide (M0O3) , molybdenum dioxide (MoO2) ,
molybdenum monoxide (MoO) , vanadium pentoxide (V205) , vanadium
tetroxide (V2O4) , vanadium trioxide (V2O3) , bismuth oxide (Bi2O3) ,
ceriumoxide (CeO2) , copperoxide (CuO) , niobiumpentoxide (Nb205) ,
stibium oxide (antimony oxide: Sb2O3) , silicon monoxide (SiO) ,
gadolinium oxide (Gd2C>3) , tantalum oxide (Ta205) , yttrium oxide
(Y2O3) , nickel oxide (NiO) , samarium oxide (Sm2O3) , iron oxide
(Fe2O3) , tin oxide (SnO2) , aluminum oxide (A12O3) , silicon dioxide
(SiO2) , chromium oxide (Cr2O3) , zinc oxide (ZnO), indium oxide
(ln2O3) , zirconium oxide (ZrO2) , magnesium oxide (MgO), barium
sulfate (BaSO4) , calcium sulfate (CaSO4) , calcium carbonate
(CaCO3) , calciumsilicate (CaSi2O5) , magnesiumcarbonate (MgCO3) ,
lithium carbonate (Li2CO3) , sodium carbonate (Na2CO3) , cobalt
carbonate (CoCO3) , strontium carbonate (SrCO3) , nickel carbonate
(Ni2CO3), bismuth carbonate ((BiO)2CO3), aluminum phosphate
(AIPO4) , barium hydrogen phosphate (BaHPO4) , lithium phosphate
(Li3PO4) , zinc citrate (Zn3 (C6H5O7) 2) , zinc borate (2Zn0-3B2O3) ,
barium borate (BaB4O7) , uranium oxide (U308) , and the like may
be mentioned as examples.
Among these, as the inorganic resist which causes a
difference in solubility in the developing solution (selection
ratio) under the effect of active energy rays such as laser,
electron beam, ionbeam, hydrogen plasma, ultraviolet radiation,
visible radiation and infrared radiation, those containing, as
the metallic element in themetal oxide, tungsten (W) , molybdenum
(Mo) , vanadium (V) , tantalum (Ta) , iron (Fe), nickel (Ni), copper
(Cu) , titanium (Ti), ruthenium (Ru) , silver (Ag), zinc (Zn),
aluminum (Al), thallium (Tl), boron (B) , germanium (Ge), niobium
(Nb) , silicon (Si), uranium (U) , tellurium (Te), bismuth (Bi) ,
cobalt (Co), chromium (Cr), tin (Sn), zirconium (Zr) ormanganese
(Mn), are known. Even among these, tungsten (W), molybdenum
(Mo) , vanadium (V) , tantalum (Tl) and iron (Fe) can be used as
the metallic element, and in particular, metal oxides containing
tungsten (W) , molybdenum (Mo) and vanadium (V) are suitably used
as the inorganic resist layer.
As for the method for forming the inorganic resist layer, there can be used, as dry methods, CVD methods (Chemical Vapor Deposition: a technology of precipitating a thin film from a gas phase by utilizing a chemical reaction) such as thermal CVD, plasma CVD and photo CVD, as well as PVD methods (Physical Vapor Deposition: a technology of forming a thin film by physically aggregating a vaporized material on a substrate in vacuo) such as vacuum deposition, plasma-assisted deposition, sputtering and ion plating. Also, as wet methods, there can be used coating methods such as bar coating, spin coating and screen printing,
as well as the LB (Langmuir Blodgett) method, chemical precipitation, anodic oxidation, electrolytic precipitation, and the like.
Thecompositionalratioof oxygen (0) tothemetallicelement is not necessarily required to be stoichiometric, and any value can be taken within the range up to the maximum oxidation number that can be adopted by the metallic element. For example, in the case of tungsten oxide, WOX can take any value of x within the range of 0 < x < 3.
The method of adjusting the amount of oxygen which constitutes the metal oxide to be used as the inorganic resist, can be appropriately selected in accordance with the respective film forming methods. For example, in the case of performing film formation by a sputtering method, a method of forming a film by subj ecting a metal target which does not contain oxygen, to reactive sputtering with a gas containing oxygen; a method of forming a film by sputtering a target formed from a metal oxide having controlled oxygen content, with an inert gas; and the like can be employed.
(1-2) Developing solution
Next, the developing solution used for developing the above-described inorganic resist will be described.
The developing solution according to the first embodiment of the present invention is a method of adding, to an alkaline aqueous solution, an element and/or compound which is reactive with this alkaline aqueous solution, producing a salt having a development accelerating action (development accelerating
agent) in the system, and if necessary, removing the residues by a method such as filtration, to obtain a developing solution. Hereinafter, the development accelerating agent and the alkaline aqueous solution will be described in sequence.
(Development accelerating agent)
As for the element or compound of which the reaction product with an alkaline aqueous solution manifests a development accelerating action, forexample, the f ollowingmaybementioned.
Examples of the element which directly reacts with an alkaline aqueous solution, include amphoteric elements such as aluminum (Al), zinc (Zn), tin (Sn) and lead (Pb), or silicon (Si) and the like.
Examples of the compound which acts as an acid in an alkaline aqueous solution, include weakly basic compounds, acidic oxides, amphoteric oxides, amphoteric hydroxides, amphoteric electrolytes, and the like.
The weakly basic compounds refer to compounds which exhibit basicity when dissolved in an aqueous solution, but react with strong alkalis such as hydroxides, and for example, ammonium hydrogen carbonate ((NH4)HCO3), tetramethylammonium hydrogen carbonate ([ (CH3) 4N]HCO3) , tetraethylammonium hydrogen carbonate ([(C2H5) 4N]HCO3) , tetrapropylammonium hydrogen carbonate ( [ (C3H7) 4N] HCO3) , lithium hydrogen carbonate (LiHCO3) , sodiumhydrogencarbonate (NaHCO3) , potassiumhydrogencarbonate (KHCO3) , sodium hydrogen phosphite (NaHPHO3) , disodium hydrogen phosphate (Na2HPO4) , sodium dihydrogen phosphate (NaH2PO4) , dipotassium hydrogen phosphate (K2HPO4) , potassium dihydrogen
phosphate (KH2PO4) , diammonium hydrogen phosphate ( (NH4)2HPO4) , ammonium dihydrogen phosphate (NH4H2PO4), ammonium lithium hydrogen phosphate ( (NH4) LiHPO4) , ammonium sodium hydrogen phosphate ( (NH4) NaHPO4) , ammonium potassium hydrogen phosphate
( (NH4)KHPO4) , diethylammonium dihydrogen phosphate
(C4HnN-H2PO4) , tetrabutylammonium dihydrogen phosphate
( [CH3 (CH2) 3] 4NH2P04] , ammonium hypophosphite (NH4PH2O2) , sodium hypophosphite (NaPH2O2) , and the like may be mentioned.
As the acidic oxides, for example, carbon dioxide (CO2) , silicon dioxide (SiO2), chromium (VI) oxide (CrOs) , phosphorus
(V) oxide (P2O5), boron oxide (B2O3) , gallium (III) oxide (Ga2O3) , sulfur dioxide (SO2) , sulfur trioxide (SO3) , nitrogen dioxide
(NO2) , nitrogentrioxide (NO3) , tungstentrioxide (WO3) , manganese trioxide (MnO3) , vanadium pentoxide (V205) , vanadium tetroxide
(V2O4) , germanium oxide (GeO2) , boric acid (H3BO3) , phosphoric acid (H3PO4) , phosphorous acid (H3PO3) , hypophosphorous acid
(H3PO2) , and the like may be mentioned.
As the amphoteric oxides, for example, aluminum oxide
(AI2O3) , arsenicoxide (As2O3) , zincoxide (ZnO) , leadoxide (PbO) , tin oxide (SnO) , chromium (III) oxide (Cr2O3) , and the like may be mentioned.
As the amphoteric hydroxides, for example, aluminum hydroxide (A1(0H)3), zinc hydroxide (Zn(OH)2), tin hydroxide
(Sn (OH) 2) , leadhydroxide (Pb (OH) 2) , andthelikemay bementioned. As the amphoteric electrolytes, there may be mentioned those compounds which simultaneously have a basic group (-NH2) and an acidic group (-COOH) in one molecule, such as amino acids.
When solutions obtained by dissolving these elements or compounds in an alkaline aqueous solution or by reacting the elements or compounds with an alkaline aqueous solution, are titrated with an acid, in many cases, a point of neutralization appears, which is different from the point of neutralization of the alkali source. These generally act as a buffering agent with respect to the acid, and in the titration curves (pH) , the points of neutralization of the development accelerating agent and the acid often appear as an inflection point accompanied by a gentle curve. As will be described later, these additives, or the reaction products of the additives and the alkali source, are believed to have strong affinity to WO3, M0O3 and the like, whicharethedissolublecomponents of inorganicresistmaterials, and since the additives or the reaction products have an effect of enhancing the solubility of the dissoluble components of the inorganic resist in the developing solution, the additives or the reaction products are speculated to act as development accelerating agents. The suitable amount of incorporation of these elements or compounds which are used as the development accelerating agents, into the developing solution, can be appropriately adjusted and determined according to the desired rate of development. Furthermore, these elements or compounds can be used individually alone, and also as mixtures of two or more species.
Here, even those elements which react with an alkaline aqueous solution may of ten require time to be completely dissolved and to undergo a reaction. Furthermore, the acidic oxides,
amphoteric oxides and amphoteric hydroxides do not necessarily have high solubility in alkaline aqueous solutions. For this reason, in the case of using these as the development accelerating agent, the time for preparing the developing solution can be shortened by a method of accelerating dissolution by a method such as heating or ultrasonic irradiation, as well as by a method of adding an excess amount, allowing the mixture to stand for a certain time, and removing the portion remaining after dissolution by a method such as filtration, before use. Alternatively, there can be used a method of preparing in advance a liquid obtained by dissolving the additives in an alkaline aqueous solution, and adding this liquid to anew alkaline aqueous solution to dilute the liquid.
(Alkaline aqueous solution)
The alkaline aqueous solution is not particularly limited, and any base which would even dissolve in water can also be used. As for the type of the alkaline compound which serves as the alkali source, there can be used inorganic alkali compounds such as lithium hydroxide, sodium hydroxide (NaOH), potassium hydroxide (KOH) , ammonium hydroxide (NH4OH) , lithium phosphate
(Li3PO4), trisodium phosphate (Na3PO4) , disodiurn hydrogen phosphate (Na2HPO4) , sodium dihydrogen phosphate (NaH2PO4) , tripotassium phosphate (K3PO4) , dipotassium hydrogen phosphate
(K2HPO4) , potassium dihydrogen phosphate (KH2PO4) , triammonium phosphate ( (NH4)3PO4) , diammoniumhydrogenphosphate ( (NH4)2HPO4) , ammonium dihydrogen phosphate (NH4H2PO4) , ammonium lithium hydrogen phosphate ( (NH4) 2HPO4) , ammonium sodium hydrogen
hosphate ( (NH4) NaHPO4) , ammonium potassium hydrogen phosphate ( (NH4) KHPO4) , sodium carbonate (Na2CO3) , sodium hydrogen carbonate (NaHCO3) , potassium carbonate (K2CO3) , potassium hydrogen carbonate (KHCO3) , ammonium carbonate ((NH4)2CO3), ammonium hydrogen carbonate ( (NH4)HCO3) , sodiumborate (Na2B4O7) , potassium borate (K2B4O7) , ammonium borate ( (NH4) 2B4O7) , sodium silicate (Na2SiO3) , potassium silicate (K2SiO3) , ammonium silicate ( (NH4) 2SiO3) , tetramethylammonium silicate ( [ (CH3) 4N] 2SiO3) , tetraethylammonium silicate ( [ (C2H5) 4N] 2SiO3) , tetrapropylammonium silicate ( [ (C3H7) 4N] 2SiO3) , tetrabutylammonium silicate ( [ (C4H9) 4N] 2SiO3) , and ammonia water (NH4OH); as well as organic alkali compounds such as monomethylamine (CH3NH2) , dimethylamine ((CH3)2NH), trimethylamine ( (CH3) 3N) , monoethylamine (C2H5NH2) , diethylamine ((C2H5)2NH), triethylamine ( (C2H5) 3N) , monoisopropylamine (C3H7NH2), diisopropylamine ((C3H7)2NH), triisopropylamine ( (C3H7) 3N) , n-butylamine (C4H9NH2) , monoethalamine (NH2 (C2H4OH) ) , diethanolamine (NH (C2H4OH) 2) , triethanolamine (N (C2H4OH)3), monoisopropanolamine (NH2 (C3H7OH)), diisopropanolamine (NH(C3H7OH)2) , tetramethylammonium hydroxide ((CH3)4NOH), tetraethylammonium hydroxide ( (C2H5)4NOH) , tetrapropylammonium hydroxide ((C3H7) 4NOH), tetrabutylammonium hydroxide ( (C4H9)4NOH) , and choline ( (CH3) 3N (OH) CH2CH2OH) . These can be used individually alone, or as mixtures of two or more species. The concentration of alkali is not particularly limited, but when the developing solution is titrated with an acid while development accelerating agents have been added, it is necessary
that the developing solution have a pH value higher than all of the points of neutralization of the development accelerating agents. In general, it is desirable to adjust the concentration of the alkali source so that pH 10 or higher, and preferably pH 12 or higher, is obtained. In regard to the alkali aqueous solution in which these alkali sources have been dissolved, if a solution having a development time which is long to a certain extent, while not having development accelerating agents incorporated thereinto, is used, the scope of the adjustment of the development time by means of development accelerating agents is broadened, and thus it becomes easy to set the development time as desired, as well as it becomes easy to secure a margin for the development time. In this regard, it is preferable to employ water-soluble ammonium compounds such as tetramethylammonium hydroxide, ammonia water, tetraethylammoniumhydroxide, tetrabutylammoniumhydroxide and tetra-n-propylammonium hydroxide as an alkali source.
Generally, with regard to the organic resists, when pH is high, the penetrating power into the resist becomes stronger, and the organic resists frequently cause problems such as detachment. However, the inorganic resists have a smaller risk of penetration such as permeation through the film. Therefore, it is possible to use the developing solution at high pH, so as to extend the use life of the developing solution.
Here, the metal oxide part of the inorganic resist which is dissolved as a result of development, for example, WO3, is solvated in the alkaline aqueous solution. As for the form of
solvate, structures such as sodium phosphotungstate • n hydrate (Na3PO4-12WO3-nH2O) , ammonium phosphotungstate • n hydrate (2 (NH4) 3P04-12WO3-nH2O) , ammonium tungstate pentahydrate (5 (NH4)20-12WO3-5H2O) , and sodium tungstate (VI) • dihydrate (Na2WO4* 2H20) , are known as stable compounds. Thus, it is conceived that development proceeds when the alkali source directly acts on the dissoluble components (acid components) such as WO3 in the inorganic resist, and is hydrated.
The developing solution can be used, with appropriate surfactants, organic solvents, defoaming agents and the like being incorporated therein, for the purpose of enhancing the wettability of the inorganic resist, or defoaming. The temperatureofthedevelopingsolutionisnotparticularlylimited, but in order to adjust the dissolution rate of the thin film, the temperature can be appropriately adjusted.
(1-3) Reaction mechanism of inorganic resist Next, the speculative reaction mechanism of the inorganic resist will be explained.
In the case of using a metal oxide as a thermosensitive inorganic resist, it is thought that local thermal expansion at the site of laser irradiation of the resist film, redistribution of oxygen (oxidation/reduction reaction) between the molecules constituting the inorganic resist, and release of oxygen gas due to decomposition of the metal oxide occur all at the same time. Furthermore, due to an increase in the rapid molecular vibration which is caused by localized strong heating for a short time,instantaneousvolume expansionandchemical reactions occur
at the site of laser irradiation, and fine cracks are generated.
Hereinafter, the speculative reaction mechanism of the inorganic resist will be described with reference to Fig. 1.
When the inorganic resist 1 is irradiated with laser radiation L (see Fig. 1A) , among the molecules 2 (for example, amorphous WO1.5) strongly heated by the irradiation of laser radiation L, some of them release oxygen to become reduced bodies 3 (for example, amorphous WO), while some of them accept the oxygen to become oxidized bodies 4a (for example, amorphous WO3) or oxidized bodies 4b (for example, crystalline WO3) (see Fig. IB) . In the metal oxides used as the inorganic resist, such as tungsten oxide (WOX, 0 < x < 3) or molybdenum oxide (MoOx, 0 < x < 3) , a compound having a high oxidation level (x is large) has high alkali solubility, while a compound having a low oxidation level (x is small) has low alkali solubility. Therefore, at the site of irradiation with laser radiation, the oxidized parts have improved alkali solubility, while the reduced parts have decreased alkali solubility. As such, when a mixture in which the oxidation product and the reduction product are co-present, is subjected to development by means of alkali development, the acidic product is dissolved, and the reduction product which has been dispersed therein is also eliminated together (see Fig. 1C) . As a result, it is thought that the entire site which has induced the oxidation/reduction reaction is developed, and a shape pattern is formed.
During the oxidation/reduction reaction, the reduced bodies 3 have their volume reduced as compared to the original
molecules, while the oxidized bodies 4a and 4b have the volume increased. Here, to take an example of the specific weights of metal oxides, crystalline W30: 14.7 g/cm3, crystalline WO2: 10.8 g/cm3, crystalline WO3: 7.2 g/cm3, amorphous WO3: 6.8 g/cm3, crystalline Mo02: 6.5 g/cm3, and crystalline Mo03: 4.7 g/cm3, andthus, asoxidationprogresses, thespecificweightisdecreased (the volume is increased) . Also, when the formed amorphous metal oxide layer is heated by irradiation with laser radiation, a large number of crystalline particles are generated in and around the laser irradiated parts . Here, when amorphous particles and crystalline particles are compared in terms of the alkali solubility, in the case of compounds of the same oxidation level, for example, between WO3, the portion which does not form crystallinelattices, thatis,theamorphousparticles,dissolves in alkali within a shorter time than crystals. On the other hand, this property is utilized in the formation of patterns ofnegative type resist. It is contemplatedthat the simultaneous occurrence of such increase and decrease of volume and the generation of crystalline particles in a short time, is also causative of crack generation.
It is also contemplated that the oxygen released as a result of decomposition of metal oxide by strong heating, enlarge the cracks 5, or produce voids between crystals. Here, in regard to the metal oxide such as tungsten oxide (WOx, 0 < x < 3) or molybdenum oxide (MoOx, 0 < x < 3) , a compound having a relatively high oxidation level, for example, with x being 2 or greater, is thought to be associated with a higher proportion of oxygen
gasgeneratedduetotheheatingbyirradiationwithlaserradiation, and this is believed to cause enlargement of cracks 5 orproduction of voids between crystals, thereby inducing large expansion of the volume (Fig. IB, bulge 6) . For this reason, the bulge at the edge part of the shape pattern obtained after development (Fig. 1C, bulge 6) also becomes larger. On the other hand, a compound having a relatively low oxidation level, for example, with x being less than 2, is thought to be associated with a smaller amount ofgenerationofoxygen gas. Therefore, thevolume expansion at the site of irradiation with laser radiation is also diminished, and the bulge at the edge part of the shape patternobtainedafter development (Fig. 1C, bulge 6) alsobecomes smaller.
The generated cracks 5 or the voids between crystals are thought to contribute in enhancing the effect of making the developing solution to penetrate into the inside. Thus, the more the metal oxide with higher oxidation level is used, the further the alkali solubility is enhanced.
Furthermore, in the case of forming an inorganic resist layer formed from a metal oxide on a base material, it is preferable to appropriately form a foundation layer aiming for heat storage (heatstoragelayer) onthebasematerial, andtoformtheinorganic resist layer thereon. It is because the exposure sensitivity can be increased.
(1-4) Reaction between inorganic resist and developing solution
Next,the speculative reactionbetweenthe inorganicresist
material and the developing solution will be described.
The inorganic resist corresponds to an inorganic compound having a low molecular weight and adopting an amorphous or crystalline form. Therefore, in the development of the inorganic resist, a relatively simple neutralization reaction in which these inorganic resist molecules and the alkali component of the developing solution react, is the main process . Therefore, it is possible to shorten the development time by adding a compound having a reaction accelerating action or a catalytic action, or the like into the developing solution.
Although the mechanism by which the compound added to the alkaline aqueous solution accelerates the reaction is not clear, it is speculated to be approximately as follows.
The compound added to the alkaline aqueous solution reacts with the alkali source and forms a salt. For example, when silicon (Si), carbon dioxide gas (CO2) and tetramethylammonium hydrogen carbonate ([(CH3) 4N]HCO3) are dissolved in an aqueous solution of tetramethylammoniumhydroxide ( (CH3)4N-OH) , they respectively form salts such as tetramethylammonium metasilicate ( [ (CH3) 4N] 2O- SiO2) and tetramethylammonium carbonate ( [ (CH3) 4N] 2CO3) by the reactions such as follows.
Si + 2(CH3)4N-OH + H20 → [ (CH3) 4N] 20-Si02 + H2 t
CO2 + 2 (CH3) 4N • OH → [ (CH3)4N]2CO3 + H20
[ (CH3)4N]HCO3 + (CH3)4N-OH → [ (CH3) 4N] 2CO3 + H20
In the following, the speculative development mechanism of the inorganic resist will be described, with reference to Fig. 2, by taking the case in which tetramethylammonium
metasilicate is produced in an aqueous solution of tetramethylammonium hydroxide, as an example. Here, in Fig. 2, description of water molecules is omitted. Also, in Fig. 2, "TMA" indicates (CH3)4N.
It is conceived that, in the developing solution, tetramethylammonium metasilicate forms a kind of intermediate with an acidic substance (WO3) which has been produced in the inorganic resist as a result of the latent image formation of the inorganic resist. Since a structure such as silicotungstic acid (Si02-12WO3-26H20) or sodium tungstate (VI) dihydrate (Na2WO4- 2H20) exists as a water-soluble, stable compound, it is thought that the intermediate also forms a bond between WO3 and Si02, and between WO3 and (CH3)4N-OH or (CH3) 4N-ON (CH3) 4. Subsequently, this intermediate is hydrated, and seeps out into the developing solution. Furthermore, this solvate delivers WO3 to tetramethylammonium hydroxide ( (CH3)4N*OH) , which is the alkali source in the developing solution, to separate from Si02, and Si02 in turn becomes able to form an intermediate with WO3 of the inorganic resist. The WO3 seeped out from the inorganic resist is speculated to be solvated in the solvent in a form such as [ (CH3) 4N] 2O* WO3. Thus, it is speculated that the added salts are repeatedly used as a medium which delivers WO3 from theinorganicresisttothealkali sourceinthedevelopingsolution, almost without being consumed. That is, it is speculated that there exists a mechanism in which SiO2 acts as a kind of catalyst. When the development accelerating agent is tetramethylammonium carbonate, CO2 serves as the catalyst. It is conceived that
because of such mechanism, as is the case of conventional methods, a constant rate of development is maintained by replenishing the worn out developing solution with a new developing solution or alkali. Therefore, when a compound which brings about such catalytic action is incorporated into the developing solution as a development accelerating agent, and the development time is set to be constant from the beginning, the developing solution may maintain a stable rate of development all the time.
When a developing solution incorporated with a development accelerating agent is titrated with an acid such as hydrochloric acid, inmanycases,thepointsofneutralizationofthedevelopment accelerating agent and the acid appear as an inflection point accompanied by a gentle curve in the titration curve (pH) . It is conceived that within this region, the neutralization reaction proceeds while the development accelerating agent acts as a kind of buffering agent to the acid. If the developing solution is prepared such that it spH is higher than the point of neutralization of the alkali source of the developing solution and all of the points of neutralization, the development accelerating agent exerts action on the acid components such as WO3 which has been generated at the site of laser irradiation of the inorganic resist. Therefore, it is necessary to establish the pH of the developing solution to be higher than the point of neutralization of the alkali source of the developing solution and all of the points of neutralization of the development accelerating agents.
Fig. 3showsatitrationcurve(pH)obtainedwhenadeveloping solution prepared by dissolving tetramethylammonium carbonate
in an aqueous solution of tetramethylammonium hydroxide, was tit rated with dilute hydrochloric acid. The reactions occurring intherespectiveregionsofthetitrationcurve(pH)arespeculated to be as follows.
To first inflection point: [(CH3) 4N- 0] 3COH + HC1 → [ (CH3)4N]2CO3 + [(CH3)4N]Cl + H2O
First to second inflection point: [ (CH3) 4N] 2CO3 + HC1 → (CH3)4NHCO3 + [(CH3)4N]C1
Second to third inflection point: (CH3)4NHCO3 + HCl → [ (CH3)4N]C1 + H20 + CO2
A substance which acts as an acid to the alkali source of the developing solution, reacts therewith to form a solvate, and manifests a buffering action in the alkaline region, can also act as a development accelerating agent. For example, WO3, which is also a dissoluble component in the inorganic resist, is thought to be in a solvated state in an aqueous solution of (CH3) 4N • OH, which is a developing solution, to a structure such as [ (CH3) 4N] 20- WO3-nH20. When the product obtained by dissolving WO3 in an aqueous solution of (CH3)4N-OH is titrated with hydrochloric acid, an inflection point accompanied by a gentle curve appears near pH 11, in addition to the point of neutralization of (CH3)4N-OH, which appears near pH 7 . This shows an end point of the neutralization reaction between the reactants of the development accelerating agent and the alkali source, and hydrochloric acid. Similarly to the case of [ (CH3) 4N] 20-Si02 or [(CH3) 4N]20-CO3, it is speculated that a solvate such as [ (CH3) 4N] 20-WO3-nH20itself actsonWO3, whichisanacidicsubstance
in the inorganic resist. It is thought that the solvate which acts as the development accelerating agent as such, is repeating a cycle such as of trapping WO3 in the inorganic resist to elute it into the developing solution, and then delivering WO3 to the alkali source of the developing solution. The phenomenon in which the rate of development keeps increasing while the development of the resist master which makes use of WOX (0 < x < 3) as the inorganic resist, is repeated, is presumed to be the result of WO3 acting in such manner as a kind of autocatalyst. As such, an element or compound which forms a reaction productoracoordinationproductinthealkalineaqueous solution, can be used as a development accelerating agent, if the element or compound is capable of manifesting a pH buffering action in the alkaline region. A developing solution formed by adding such element or compound shows, when titrated with an acid, a region indicating the neutralization reaction of the acid by additives, in the titration curve (pH) . This frequently appears as an inflection point accompanied by a gentle curve in the titration curve (pH) , and frequently appears as the minimum value in the titration curve (conductivity) . In other words, it can bepredictedbeforeactuallyperformingdevelopment, astowhether a salt or the like can be utilized as a development accelerating agent, byverifyingwhethersuchregionwouldappearinthealkaline region through titration.
(1-5) Method for producing resist master Next, an example of the method for producing a resist master by using the above-described inorganic resist and developing
solution, will be described with reference to Fig. 4 and Fig. 5. This method for producing a master is suitable for the production method for a master for high density optical disk such as Blu-ray Disc (registered trademark) . Furthermore, this method for producing a master is not intended to be limited to the optical disc type, but can also be used in the production of a master of any of the read-only type, the data addition type and the rewritable type.
To the alkaline aqueous solution, a development accelerating agent is added in an amount of incorporation that has been confirmed to be capable of obtaining stable development properties.
As shown in Fig. 4A, a flat and smooth substrate 11 made of, forexample, siliconorthelike,isproduced. Then,according to necessity, as shown in Fig. 4B, a foundation layer 12 is formed on the substrate 11 by, for example, a sputtering method. As forthematerialconstitutingthe foundationlayer 12,forexample, a mixture of zinc sulfide and silicon dioxide (ZnS-Si02 mixture) , tantalum pentoxide (Ta205) , titanium dioxide (TiO2) , amorphous silicon (a-Si), silicon dioxide (SiC>2) , silicon nitride (SiN) , and the like may be mentioned, and from the viewpoint of good exposure sensitivity, materials having high heat storability, suchas amixture of ZnS-Si02, tantalumpentoxide (Ta23) , and the like may be mentioned.
Asforcarbonates, forexamples, lithiumhydrogencarbonate
(LiHCO3) , sodiumhydrogen carbonate (NaHCO3) , potassiumhydrogen carbonate (KHCO3) , lithium carbonate (Li2CO3) , sodium carbonate
(Na2CO3) , potassiumcarbonate (K2CO3) , rubidiumcarbonate (Rb2CO3) , cesium carbonate (Cs2CO3) , and the like may be mentioned.
Lithium tetraborate (Li2B4O7) , sodium tetraborate (Na2B4O7) , potassium tetraborate (K2B4O7) , disodium tetraborate (Na2B4O7) , sodium tetraphenylborate (NaB (C6H5) 4) , lithium borate (Li2B4O7) , sodium borate (Na2B4O7) , potassium borate (K2B4O7) , and the like may be mentioned.
As for phosphates, for example, sodium tripolyphosphate
(Na5P3Oio) t sodiumdiphosphate (Na4P2O7) , potassiumpyrophosphate
(K4P2O7) , tetrasodium pyrophosphate (Na4P2O7) , sodium pyrophosphate (Na4P2O7) , sodium metaphosphate ((NaPO3)n), potassium metaphosphate ((KPO3)n), lithium phosphate (Li3PO4) , trisodium phosphate (Na3PO4) , tripotassium phosphate (Ka3PO4) , sodium hydrogen phosphite (NaHPHO3) , dipotassium phosphite
(K2PHO3) , sodium hypophosphite (NaPH2O2) , sodium tungstophosphate (Na3 (P04 • 12WO3) ) , disodium hydrogen phosphate
(Na2HPO4) , sodium dihydrogen phosphate (NaH2PO4) , dipotassium hydrogen phosphate (K2HPO4) , potassium dihydrogen phosphate
(KH2PO4) , ammonium lithium hydrogen phosphate (LiNH2HPO4) , ammonium sodium hydrogen phosphate (NaNH4HPO4), ammonium potassium hydrogen phosphate (NaNH4HPO4) , and the like may be mentioned.
As forhalides, forexample, lithium fluoride (LiF), sodium fluoride(NaF),potassiumfluoride(KF),rubidiumfluoride (RbF), cesium fluoride (CsF) , lithium chloride (LiCl), sodium chloride
(NaCl), potassium chloride (KC1), rubidium chloride (RbCl), cesium chloride (CsCl), lithium bromide (LiBr) , sodium bromide
(NaBr) , potassiumbromide (KBr), rubidiumbromide (RbBr), cesium bromide (CsBr), lithium iodide (Lil), sodium iodide (Nal), potassiumiodide(KI),rubidiumiodide(Rbl),cesiumiodide (Csl), and the like may be mentioned.
As for nitrates, for example, lithium nitrate (LiNO3) , sodiumnitrate (NaNO3) , potassiumnitrate (KNO3) , rubidiumnitrate
(RbNO3) , cesium nitrate (CsNO3) , and the like may be mentioned.
As for sulfates, for example, lithium sulfate (Li2SO4) ,
sodium sulfate (Na2SO4) , potassium sulfate (K2SO4) , rubidium
nitrate (Rb2SO4) , cesium nitrate (Cs2SO4) , and the like may be
mentioned.
As for hydroxides, forexample, lithium hydroxide (LiOH) , sodium hydroxide (NaOH), potassium hydroxide (KOH), rubidium hydroxide (RbOH) , cesium hydroxide (CsOH) , and the like may be
mentioned.
In addition to these, as organic acid salts, for example, lithiumacetate (CH3COOLi), sodium acetate (CH3COONa) , potassium acetate (CH3COOK), lithium formate (HCOOLi), sodium formate (HCOONa), potassium formate (HCOOK), potassium benzoate (C6H5COOK), sodium benzoate (C6H5COONa), triammonium citrate ( (NH4) 3C6H5O7) , diammonium hydrogen citrate ( (NH4) 2HC6H5O7) , potassium dihydrogen citrate (KH2C6H5O7) , dipotassium hydrogen citrate (K2HC6H5O7) , tripotassium citrate (K3C6H5O7) , trisodium citrate (Na3C6H5O7) , disodiumhydrogencitrate (Na2HC6H5C>7) , sodium dihydrogen citrate (NaH2C6H5O7) , lithium citrate (Li3C6H5O7) , ammonium tartrate ( (NH4)2C4H4O6), ammonium hydrogen tartrate (NH4HC4H4O6) , potassium tartrate (K2C4H4O6) , potassium hydrogen tartrate (KHC4H40e) , sodium hydrogen tartrate (NaHC4H4O6) , sodium potassium tartrate (NaKC4H4C>6) , sodium tartrate (Na2C4H4O6) , lithium tartrate (Li2C4H4O6) , and the like, water-soluble salts which serve as the sources of alkali metal ions can be used. A suitable amount of incorporation into a developing solution, of these salts which are used as development accelerating agents, can be appropriately adjusted and determined in accordance with the desired rate of development. These salts can also be used individually alone, or as mixtures of two or more species.
(Alkaline aqueous solution)
In regard to the alkaline aqueous solution, an aqueous solution formed from an alkali hydroxide which does not contain an alkali metal, can be used. As for the type of the alkaline compound which serves as the alkali source, tetramethylammonium
hydroxide ((CH3)4NOH), tetraethylammonium hydroxide ( (CH2H5) 4NOH) , tetrapropylammonium hydroxide ( (C3H7) 4NOH) , tetrabutylanimonium hydroxide ( (C4H9) 4NOH) , choline ( (CH3) 3N (OH) CH2CH2OH) , and the like can be used. These can be used individually alone, or as mixtures of two or more species. The concentration of these hydroxide ion sources is not particularly limited, but it is necessary to establish the pH value to be higher than the point of neutralization of the development accelerating agent, when the alkaline aqueous solution is titrated with an acid while the development accelerating agent has been added.
Generally, it is desirable to adjust the concentration of the hydroxide ion source to obtain pH 10 or higher, andpreferably pH 12 or higher.
Since these aqueous solutions of tetraalkylammonium hydroxide do not have such high developing power against inorganic resist by themselves, when only these are put into use, relatively long time is required for development. In that regard, the scope for adjusting the rate of development can be taken broadly, by adding only a controlled quantity of an alkali metal compound as the development accelerating agent.
(3-2) Reaction between inorganic resist and developing solution
The mechanism by which the development accelerating agent added to an alkaline aqueous solution accelerates the reaction, is obscure, but it is speculated to be approximately such as follows.
For example, while the development time is not shortened even though tetramethylammonium chloride ((CH3)4N'C1) is dissolvedinanaqueous solutionoftetramethylammoniumhydroxide ( (CH3) 4N- OH) , the development time is shortened to a large extent when sodium chloride (NaCl) is added. From this, it is understood that the development accelerating action depends largely on the nature of the cation moiety.
A case of using tetramethylammonium hydroxide as the teraalkylammonium hydroxide which is used as the hydroxide ion source, and using sodium chloride as the source of alkali metal ions, will be described as an example . The added sodium chloride dissolves inanaqueous solutionof tetramethylammoniumhydroxide, and nearly completely dissociates into a cation (Na+) and an anion (Cl~) . The acidic substance (WO3) produced in the inorganic resist as a result of the latent image formation of the inorganic resist, is attached by hydroxide ions (0H~) in the solution, and dissolves. At this time, under the action of cations such astetramethylammoniumions ((CH3) 4N+) andsodiumion,dissolution of W03 is accelerated. This is speculated such that during the time period in which WO3 leaves from the inorganic resist and is stabilized by being solvated, a kind of intermediate state is formed, and since the rate of forming this intermediate state is faster with sodium ions (Na+) than with tetramethylammonium ions ( (CH3) 4N+) , or since the penetrating power into the inorganic resist film is greater for sodium ions (Na+) than for tetramethylammonium ions ( (CH3) 4N+) , a development accelerating effect is exhibited.
Here, tungsten oxide (W03) which is a dissoluble component of the inorganic resist, exhibits water-solubility in the state of an ammonium salt, an alkali metal salt, a magnesium salt or the like, but is nearly insoluble in the state of other metal salts. In the case where the element contained in the cation moiety of the development accelerating agent is an alkaline earth metal such as calcium or magnesium, when the development accelerating agent is incorporated into a strongly alkaline aqueous solution, calcium hydroxide (solubility in water: 1.7%, 20°C) ormagnesiumhydroxide (solubilityinwater: 0.0009%, 18°C) , which are allscarcelysoluble inwater, is formedandprecipitates out, and desired characteristics cannot be obtained. Therefore, in the present invention, the cation moiety of the development accelerating agent is defined to include an alkali metal.
Hereinafter, the present invention will be specifically described by way of Examples, but the present invention is not intended to be limited only to these Examples. In addition, Example 1 to Example 6 correspond to the first embodiment, Example 7 to Example 28 correspond to the second embodiment, and Example 29 to Example 42 correspond to the third embodiment.
Comparative Example 1>
The composition of the developing solution of Comparative Example 1 and the method of evaluation will be shown in the following.
Additive: None
Alkali source: Tetramethylammonium hydroxide
Evaluation: Development, titration
(Titration of developing solution)
As an alkaline aqueous solution, a 2 . 38 wt% aqueous solution of tetramethylammonium hydroxide (Tokyo Ohka Kogyo Co., Ltd., NMD-3) was provided, and this was used as a developing solution. Subsequently, this developing solution was titrated with 0.5 normal hydrochloric acid, and the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity was determined. The results are presented in Fig. 7. Here, the measurement was carried out by using a dilution prepared by adding 50 ml of pure water to a 10-ml sample of the developingsolution. Thearrows inFig. 7 areprovidedtoindicate which titration curve is associated with which, between pH and conductivity. The arrows for the titration curves given hereafter indicate the same as in Fig. 7. (Resist master production process)
A resist master was produced as follows. First, a 100-nm foundation layer formed from amorphous silicon was formed on a substrate by a sputtering method. Here, this foundation layer is for the heat of the laser radiation irradiated on the inorganic resist layer to be efficiently accumulated.
The conditions for film production of the foundation layer will be shown below.
Substrate: 8-inch silicon wafer
Target material: Silicon
Film producing gas: Argon (Ar)-26 [SCCM]
Gas pressure for film production initiation: 5.0xl0~4 [Pa]
Film producing power: DC 135 [W]
Subsequently, an inorganic resist layer having a thickness of 25 ran was formed on the foundation layer by a sputteringmethod.
The conditions for film formation of the inorganic resist layer will be shown below.
Target material: Tungsten (W)/molybdenum (Mo)/oxygen (0) = 32/8/60 (ratio of number of atoms)
Film producing gas: Argon (Ar)-26 [SCCM]
Gas pressure for film production initiation: 5.0xlCT4 [Pa]
Film producing power: DC 135 [W]
(Exposure process)
Subsequently, exposure was performed by irradiating the inorganic resist layer with laser radiation, while rotating the resist master obtained as described above.
The condition for exposure of the inorganic resist layer will be shown below.
Light source: Semiconductor laser (wavelength 405 [nm] )
Object lens: NA = 0.9
Resist master feed speed: 0.32 [(im/revolution]
Spindle : CLV(ConstantLinerVelocity)mode 4.9 [m/seconds] (Development process)
Subsequently, the exposed inorganic resist layer was subjected to development, to produce a DC groove pattern.
The conditions for development of the inorganic resist layer will be shown below.
Developing solution temperature: 26°C
Development method: Continuous flow of the developing solution onto the resist master
Here, the development process will be described in more detail. First, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide was placed in a developing tank (manufactured by Sony Disc & Digital Solutions, Inc., PTR3000), and was maintained at 26°C. Subsequently, the inorganic resist master was mounted on a rotating stage, was subjected to processes of pre-rinse, development and post-rinse, while the rotation was maintained at 400 rpm, and then was finally dried by shaking off at 1800 rpm.
The conditions for process treatment of pre-rinse, development and post-rinse will be shown below.
Pre-rinse: Incessant flow of pure water over 60 seconds.
Development: Incessant flow of the developing solution over an established time (three points between 360 seconds to 480 seconds).
Post-rinse: Incessant flow of pure water over 18 0 seconds .
As described above, a desired resist master for optical disc was obtained.
(AFM measurement)
Subsequently, the grooves formed on the respective inorganic resist masters were measuredby using AFM (Atomic Force Microscope) . The results are presented in Table 1 and Fig. 6A to Fig. 6C. Here, the time [seconds] in which a shape pattern sufficiently dissolves down to the resist bottom so that the side geometry becomes linear, and the half-width of the groove width becomes about 160 nm, was defined as the optimum development time. Accordingly, the optimum development time for a developing
solution which is not added with a development accelerating agent is 420 seconds.
Furthermore, the developing solution used in the development was titrated with hydrochloric acid, and the relationship between the amount of dropwise addition of hydrochloricacidandthepHaswellas conductivitywasdetermined. The results are presented in Fig. 7. Here, the measurement was carried out by titrating a dilution which was prepared by adding 50 ml of pure water to a 10-ml sample of the developing solution, with 0.5 normal hydrochloric acid.
The composition of the developing solution of Comparative Example 2 and the method of evaluation will be shown in the following.
Additive: None
Alkali source: Sodium hydroxide
Evaluation: Development, titration
A resist master was obtained by carrying out the resist master production process and exposure process in the same manner as in Comparative Example 1. Subsequently, a 0.2 mol/L-NaOH aqueous solution was provided as a developing solution. This was placed in a developing tank (manufactured by Sony Disc & Digital Solutions, Inc., PTR3000), and was maintained at 26°C. The resist master was developed in the same manner as in Comparative Example 1, except that this developing solution was incessantly flowed, and the development time was set at three points between 30 seconds to 90 seconds. Subsequently, the grooves formed on
the inorganic resist master were measured by using AFM. The results are presented in Table 1 and Fig. 8A to Fig. 8C.
Thedeveloping solutionusedinthedevelopmentwas titrated with hydrochloric acid, and the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity was determined. The results are presented in Fig. 9. Here, the measurement was carried out by titrating a dilution which was prepared by adding 50 ml of pure water to a 10-ml sample of the developing solution, with 0.5 normal hydrochloric acid.
The composition of the developing solution of Comparative Example 3 and the method of evaluation will be shown in the following.
Additive: None
Alkali source: Trisodium phosphate■12-water
Evaluation: Development, titration
A resist master was obtained by carrying out the resist master production process and exposure process in the same manner as in Comparative Example 1.
Subsequently, a 0.2 mol/L aqueous solution of trisodium phosphate•12-water was provided as a developing solution.
This was placed in a developing tank (manufactured by Sony Disc & Digital Solutions, Inc., PTR3000), and was maintained at 26°C. The resist master was developed in the same manner as in Comparative Example 1, except that this developing solution was incessantly flowed, and the development time was set at three
points between 90 seconds to 120 seconds. Subsequently, the grooves formed on the inorganic resist master were measured by using AFM. The results are presented in Table 1 and Fig. 10A to Fig. IOC.
The developing solution used in the development was tit rated with hydrochloric acid, and the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity was determined. The results are presented in Fig. 11. Here, the measurement was carried out by titrating a dilution which was prepared by adding 50 ml of pure water to a 10-ml sample of the developing solution, with 0.5 normal hydrochloric acid.
The composition of the developing solution of Comparative Example 4 and the method of evaluation will be shown in the following.
Additive: Tetramethylammonium chloride
Alkali source: Tetramethylammonium hydroxide
Evaluation: Development, titration
A resist master was obtained by carrying out the resist master production process and exposure process in the same manner as in Comparative Example 1. Subsequently, a solution obtained by mixing tetramethylammonium chloride ( (CH3) 4N•CI) at a concentration of 10.0 g/L to a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, was provided as a developing solution. This was placed in a developing tank (manufactured bySonyDisc&DigitalSolutions,Inc.,PTR3000) , andwasmaintained
at 26°C. The resist master was developed in the same manner as in Comparative Example 1, except that this developing solution was incessantly flowed. Subsequently, the grooves formed on the inorganic resist master were measured by using AFM. The results are presented in Table 1 and Fig. 12A to Fig. 12C.
Thedeveloping solutionusedinthedevelopmentwas titrated with hydrochloric acid, and the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity was determined. The results are presented in Fig. 13. Here, the measurement was carried out by titrating a dilution which was prepared by adding 50 ml of pure water to a 10-ml sample of the developing solution, with 0.5 normal hydrochloric acid.
The composition of the developing solution of Comparative Example 4 and the method of evaluation will be shown in the following.
Additive: Tetramethylammonium tetrafluoroborate
Alkali source: Tetramethylammonium hydroxide
Evaluation: Development, titration
A resist master was obtained by carrying out the resist master production process and exposure process in the same manner as in Comparative Example 1. Subsequently, a solution obtained by mixing tetramethylammonium tetrafluoroborate ( (CH3)4N-BF4) at a concentration of 10.0 g/L to a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, was provided as a developing solution. This was placed in a developing tank (manufactured
bySonyDisc&DigitalSolutions, Inc. , PTR3000) , andwasmaintained at 26°C. Subsequently, the resist master was developed in the samemannerasinComparativeExample 1,exceptthatthis developing solution was incessantly flowed. Subsequently, the grooves formed on the inorganic resist master were measured by using AFM. The results are presented in Table 1 and Fig. 14A to Fig. 14C.
Thedevelopingsolutionusedinthe developmentwas titrated with hydrochloric acid, and the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity was determined. The results are presented in Fig. 15. Here, the measurement was carried out by titrating a dilution which was prepared by adding 50 ml of pure water to a 10-ml sample of the developing solution, with 0.5 normal hydrochloric acid.
In Example 1 to Example 6, the method of mixing an additive which forms a development accelerating agent by forming a salt with the alkali source, into an alkaline aqueous solution, and the development accelerating action exerted by the resulting developing solution, on an inorganic resist, will be described.
The composition of the developing solution of Example 1 and the method of evaluation will be shown in the following.
Additive: Silicon powder
Alkali source: Tetramethylammonium hydroxide
Evaluation: Development, titration
A resist master was obtained by carrying out the resist
master production process and exposure process in the same manner as in Comparative Example 1.
Subsequently, 1000 ml of a 2.38 wt% aqueous solution of tetramethylammonium hydroxide and 13.3 g of silicon powder were weighed in a stainless steel vat, and were stirred at 100°C on a hot stirrer. Subsequently, stirring was stopped when the silicon powder had all dissolved, and the system was cooled to room temperature. Subsequently, this was transferred to a Poly tank, and a fresh 2 . 38 wt% aqueous solution of tetramethylammonium hydroxide was added thereto to a total volume of 12 liters. The mixture was left to stand overnight at room temperature, and thenwas filtered through amembrane filter (AdvantecToyoKaisha, Ltd., VH020). The resulting developing solution was placed in a developing tank of PTR3000 and was maintained at 26°C. Subsequently, a resist master was developed under the same conditions as inComparativeExample 1,exceptthatthis developing solution was incessantly flowed, and the development time was set at three points between 240 seconds to 300 seconds. Then, the grooves formed on the inorganic resist master were measured by using AFM. The results are presented in Table 1 and Fig. 16A to Fig. 16C.
Also, the developing solution used in the development was titrated with hydrochloric acid, and the relationship between the amount of dropwise addition of hydrochloric acid and the pH as well as conductivity was determined. The results are presented in Fig. 17. Here, the measurement was carried out by titrating a dilution which was prepared by adding 50 ml of
pure water to a 10-ml sample of the developing solution, with 0.5 normal hydrochloric acid.
The developing solution of Comparative Example 1 to which a development accelerating agent had not been added, exhibited only the inflection point of tetramethylammonium hydroxide, the alkali source, as shown in Fig. 7. However, it was found that in the titration of the developing solution of Example 1 to which silicon had been added, as shown in Fig. 17, the development accelerating agent formed as a result of the reaction between the added silicon and the aqueous solution of tetramethylammonium hydroxide, caused a neutralization reaction with hydrochloric acid, and the titration curve (pH) showed an inflection point accompanied by a gentle curve at near pH 11, while the titration curve (conductivity) draws a minimum region from this point to the point of neutralization of tetramethylammonium hydroxide.
The composition of the developing solution of Example 2 and the method of evaluation will be shown in the following.
Additive: Silicon powder
Alkali source: Tetramethylammonium hydroxide
Evaluation: Titration
A 2.38 wt% aqueous solution of tetramethylammonium hydroxide was provided as an alkaline aqueous solution. To this aqueous solution, silicon (Si) powder was added to completely dissolve therein, and three types at concentrations 2.0, 4.0 and 6. 0 g/L were prepared. Then, the solutions were respectively filtered through a membrane filter (Advantec Toyo Kaisha, Ltd. ,
VH020), to obtain developing solutions. Subsequently, in the same manner as in Comparative Example 1, the relationship between the amount of dropwise addition of 0.5 normal hydrochloric acid and the pH as well as conductivity was determined for the respective developing solutions. The results are presented in Fig. 18, and a magnified view of the vicinity of the inflection point resulting from neutralization of the development accelerating agent is presented in Fig. 19. Here, Tl, T2 and T3 in Fig. 19 represent the titration curves of the developing solutions at concentration 2.0, 4.0 and 6.0 g/L, respectively.
The composition of the developing solution of Example 3 and the method of evaluation will be shown in the following.
Additive: Carbon dioxide gas (dry ice)
Alkali source: Tetramethylammonium hydroxide
Evaluation: Titration
200ml of a2.38 wt% aqueous solution of tetramethylammonium hydroxide and 0.2, 0.4 or 0.6 g of dry ice were placed and sealed in a pressure vessel made of stainless steel, and were left to standf or 2 days at roomtemperature . Subsequently, the solutions were respectively filtered through a membrane filter (Advantec Toyo Kaisha, Ltd., VH020) , to obtain developing solutions. For the respective developing solutions, the relationship between the amount of dropwise addition of 0. 5 normal hydrochloric acid and the pH as well as conductivity was determined in the same manner as in Comparative Example 1. The results are presented in Fig. 20, and a magnified view of the vicinity of the inflection
point resulting from neutralization of the development accelerating agent is presented in Fig. 21. Here, Tl, T2 and T3 in Fig. 21 represent the titration curves of the developing solutions at concentration 0.2, 0.4 and 0.6 g, respectively.
The composition of the developing solution of Example 4 and the method of evaluation will be shown in the following.
Additive: Tungsten trioxide
Alkali source: Tetramethylammonium hydroxide
Evaluation: Development, titration
A resist master was obtained by carrying out the resist master production process and exposure process in the same manner as in Comparative Example 1. Subsequently, powdered tungsten trioxide was added to a 2.38 wt% aqueous solution of tetramethylammonium hydroxide to a concentration of 2 . 5 g/L in a beaker, and the tungsten trioxide was completely dissolved while ultrasonic irradiation was performed. This was filtered through a membrane filter (Advantec Toyo Kaisha, Ltd., VH020), to obtain a developing solution. Subsequently, the resistmaster was developed under the same conditions as in Comparative Example 1, except that this developing solution was incessantly flowed at a temperature of 2 6°C, and the development time was set at three points between 60 seconds to 180 seconds. Subsequently, the grooves formed on the inorganic resist master were measured by using AFM. The results are presented in Table 1 and Fig. 22A to Fig. 22C.
The developing solution used in the development was
respectively titrated with hydrochloric acid, and the relationship between the amount of dropwise addition of hydrochloricacidandthepHaswellas conductivitywasdetermined. The results are presented in Fig. 23. The measurement was carried out by titrating a dilution which was prepared by adding 50 ml of pure water to a 10-ml sample of the developing solution, with 0.5 normal hydrochloric acid.
Here, the results obtained by metering 10 ml of a solution obtained by dissolving tungsten trioxide in the 2.38 wt% aqueous solution of tetramethylammoniumhydroxide to saturation, adding 50 ml of pure water thereto to dilute the solution, and titrating the dilution with 0.5 normal hydrochloric acid, are presented in Fig. 24.
When Fig. 23 and Fig. 24 are compared, the presence of an inflection point at near pH 11, which is hardly recognized in the solution of tungsten trioxide at a low concentration, is clearly found at a high concentration. However, when the conductivity is compared, the minimum region clearly appears in Fig. 24 as well as in Fig. 23. The developing solution can maintain stable development properties, as a result of replacing before this region is reached. Furthermore, by taking the conductivity as an index, the degree of deterioration of the developing solution can be conveniently found.
The composition of the developing solution of Example 5 and the method of evaluation will be shown in the following.
Additive: Boric acid
Alkali source: Tetramethylammonium hydroxide
Evaluation: Development, titration
A resist master was obtained by carrying out the resist master production process and exposure process in the same manner as in Comparative Example 1. Subsequently, boric acid was added to a 2 . 38 wt% aqueous solution of tetramethylammonium hydroxide, and thus a developing solution at a concentration of 5.0 g/L was obtained. Subsequently, the resist master was developed under the same conditions as in Comparative Example 1, except that this developing solution was incessantly flowed at a temperature of 2 6°C. Subsequently, the grooves formed on the inorganic resist master were measured by using AFM. The results are presented in Table 1 and Fig. 25A to Fig. 25C.
Furthermore, the developing solution used in the development was titrated with hydrochloric acid, and the relationship between the amount of dropwise addition of hydrochloricacidandthepHaswellas conductivitywasdetermined. The results are presented in Fig. 26. Here, the measurement was carried out by titrating a dilution which was prepared by adding 50 ml of pure water to a 10-ml sample of the developing solution, with 0.5 normal hydrochloric acid. (Table 1)
(Table removed)
[As to shape obtained after development] (a) From Comparative Example 1 and Comparative Example 2, it can be seen that the characteristics exhibited by pH or conductivity are almost the same, and an aqueous solution of sodium hydroxide shows markedly superior development accelerating action as compared to an aqueous solution of tetramethylammonium. That is, it can be seen that in the case of using tetramethylammonium as the cation moiety of the alkali source, the development margin is much larger than in the case of using sodium. Also in regard to the surf ace morphology obtained by development, the aqueous solution of tetramethylammonium hydroxide leads to reduced generation of irregularities. It is speculated that these actions originate from the difference inthepenetrabilitytothe inorganicresist, whichisattributable to the difference in the steric hindrance of the cation moiety. Furthermore, it is understood that, as in Comparative Example
6, in the case where sodium hydroxide and tetramethylammonium are co-present in the developing solution, the properties of sodium hydroxide which has high development accelerating action are preferentially manifested.
(b) From a comparison of Comparative Example 1, Comparative Example 4 and Comparative Example 5, it can be seen that the development time taken until the half-width of the groove width reaches about 160 nm, is almost the same. That is, it can be seen that in the developing solution to which a neutral salt formed from a strong base whose alkali component is the same as the alkali source of the developing solution, and a strong acid, such as tetramethylammonium chloride or tetramethylammonium tetrafluoroborate, has been added, an increase in the rate of development is almost not seen. On the other hand, it is also understood that, as in Comparative Example 3, in a developing solution to which an alkali metal salt such as sodium chloride has been added as a neutral salt, the rate of development increases to a large extent. However, the development time is longer than that for the case where development is carried out with the aqueous solution of sodium hydroxide of Comparative Example 2, and the surface morphology obtainable therefrom is also associated with reduced generation of irregularities. That is, Comparative Example 3 is thought to involve development in a state which is intermediate between Comparative Example 1 and Comparative Example 2 . It is speculated that this originates from the penetrating power into an inorganic resist film based on the difference in the alkali metal
concentration, or from the difference in the contribution to the stabilization of the dissolved acid component, but does not originate from catalytic action.
(c) From a comparison between Example 1 and Example 2 to Example 5, it can be seen that the development time taken until the half-width of the groove width reaches about 160 nm, is shortened, as compared to Comparative Example 1. Particularly, Example 3 exhibits a marked decrease in the development time. Therefore, it is understood that, when silicon, carbon dioxide, tungsten trioxide, boric acid and the like are incorporated as additives, they respectively exhibit different development accelerating actions.
When a resist master manufactured by forming an inorganic resist layer containing tungsten oxide as a main component on a silicon substrate, is repeatedly developed, the development time is gradually shortened proportionally to the number of development process, and converges to a certain value. This is conceived to be t he result of that tungsten oxide in the inorganic resist, silicon of the silicon substrate, and carbon dioxide gas in air separately blend in into the alkaline aqueous solution, and react with the alkali source of the developing solution to form development accelerating agents, and the development time converges to a stable value corresponding to the dissolution ratio of the three components.
[As to titration curve]
In Comparative Example 1 to Comparative Example 5, any inflection point other than that originating f romneutralization
of the alkali source does not appear on the titration curve (pH) , and the point of neutralization of pH remained almost unchanging (see Fig. 7, Fig. 9, Fig. 11, Fig. 13 and Fig. 15), whereas in Example 1 to Example 5, inflection points originating from the development accelerating agents produced in the developing solution, appear on the titration curve (pH), in addition to the point of neutralization of the alkali source (see Fig. 17 to Fig. 21, Fig. 23, Fig. 24 and Fig. 26) . Moreover, the corresponding titration curve (conductivity) has a minimum value at the part of pH inflection point. That is, for a developing solution which is obtained by adding silicon, carbon dioxide gas, tungsten trioxide, boric acid or the like, which serve as the raw materials of development accelerating agents, to an alkaline aqueous solution, the presence of additives can be confirmed by titrating with an acid and verifying any change in the shape of the titration curve. Particularly, in Example 2 and Example 3, if the dissolution concentration of silicon or dry ice is low, it becomes difficult to determine the inflection point due to the development accelerating agent from the titration curve (pH) , whereas the titration curve (conductivity) exhibits theminimumvalueinanextremelydistinct form, thusdetermination being easy. As such, for the purpose of simply detecting the state of the developing solution, measurement of conductivity is an effective method. Furthermore, by verifying whether or not an inflection point other than that originating from the alkali source appears on the titration curve (pH), it can be predicted, before actually carrying out the development of an
inorganic resist, as to whether an element or an oxide can be used as a development accelerating agent.
A resist master was obtained by carrying out the resist master production process and exposure process in the same manner as in Comparative Example 1. Subsequently, boric acid was added as a development accelerating agent to a 2 . 38 wt% aqueous solution of tetramethylammonium hydroxide, and four types of developing solutions at concentrations of 0.0, 2.5, 5.0 and 10.0 g/L were prepared. Subsequently, development of the inorganic resist master was carried out in the same manner as in Comparative Example 1, except that these developing solutions were used, and the time taken until the half-width of the groove width reached about 160 run, was determined. The relationship between the amount of addition of the development accelerating agent and the development time is shown in Fig. 27.
As shown in Fig. 27, boric acidmanifests a weak development accelerating action in a manner nearly proportional to the amount of addition. It is speculated that in the developing solution, the compound formed from tetramethylammonium hydroxide, which is the alkali source, and boric acid, acts on the dissoluble component (acid component) of the inorganic resist, and thereby development is accelerated.
In Example 7 to Example 26, the method for preparing a developing solution by using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide as an alkaline aqueous solution, and incorporating a development accelerating agent thereto, and
thedevelopmenteffectexertedbytheobtaineddevelopingsolution on an inorganic resist, will be described.
A resist master was obtained by carrying out the resist master production process and exposure process in the same manner as in Comparative Example 1. Subsequently, the development accelerating agents shown in Table 2 were added to a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, and developing solutions at a concentration of 10 g/L were prepared for the respective development accelerating agents. Subsequently, development of the inorganic resist master was performed in the same manner as in Comparative Example 1, except that these developing solutions were used, and thus desired resist masters for optical disc were obtained. Subsequently, the grooves formed on the inorganic resist masters were measured by using AFM. The results are presented in Table 2 and Fig. 28, Fig. 30, ..., Fig. 44, and Fig. 46.
Furthermore, the developing solutions used in the development were titrated with hydrochloric acid, and the relationship between the amount of dropwise addition of hydrochloricacidandthepHaswell as conductivitywasdetermined. The results are presented in Fig. 29, Fig. 31, ..., Fig. 45, and Fig. 47. Here, the measurement was carried out by titrating a dilution which was prepared by adding 50 ml of pure water to a 10-ml sample of the developing solution, with 0.5 normal hydrochloric acid.
A resist master was obtained by carrying out the resist master production process and exposure process in the same manner as in Comparative Example 1. Subsequently, the development accelerating agents shown in Table 3 were added to a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, and developing solutions at concentrations of 0.0, 2.5, 5.0 and 10.0 g/L were prepared for the respective development accelerating agents. Subsequently, development of the inorganic resist master was performed in the same manner as in Comparative Example 1, except that these developing solutions were used, and the time taken until the half-width of the groove width reached about 160 nm was determined. The relationship between the amount of additionofthedevelopmentacceleratingagent andthe development time is presented in Fig. 48 to Fig. 50. (Table 2)
(Table removed)
In Example 16, the development time has been shortened to about 1/2, as compared to Comparative Example 1. As can be seen in Comparative Example 3, since chlorine ions do not exhibit a development accelerating action, this can be judged based on the action of ammonium ions.
(Table 3) (Table removed)
InExample27,themethodforpreparingadevelopingsolution by using a 0.2 mol/L aqueous solution of trisodium phosphate as an alkaline aqueous solution, and incorporating thereto tetramethylammoniummetasilicate as a development accelerating agent, and the development effect exerted by the obtained
developing solution on an inorganic resist, will be described.
The composition of the developing solution of Example 27 and the method of evaluation will be shown in the following.
Additive: Tetramethylammonium metasilicate
Alkali source: Trisodium phosphate•12-water
Evaluation: Development, titration
A resist master was obtained by carrying out the resist master production process and exposure process in the same manner as in Comparative Example 1. Subsequently, tetramethylammonium metasilicate was added to a 0 . 2 mol/L aqueous solution of trisodium phosphate • 12-water, and a developing solution at a concentration of 10 g/L was prepared. Subsequently, development of the inorganic resist master was performed in the same manner as in Comparative Example 1, except that this developing solution was used, and a desired resist master for optical disc was obtained. Subsequently, the grooves formed on the inorganic resist master were measured by using AFM. The results are presented in Table 4 and Fig. 51.
Furthermore, the developing solution used in the development was titrated with hydrochloric acid, and the relationship between the amount of dropwise addition of hydrochloricacidandthepHaswellas conductivitywasdetermined. The results are presented in Fig. 52. Here, the measurement was carried out by titrating a dilution which was prepared by adding 50 ml of pure water to a 10-ml sample of the developing solution, with 0.5 normal hydrochloric acid.
(Table 4) (Table removed)
When Example 27 is compared with Comparative Example 3, it can be seen that, even in the case of using trisodium phosphate-12-water as the alkali source, a development accelerating effect based on the added tetramethylammonium metasilicate is manifested.
In Example28,themethodforpreparingadevelopingsolution by incorporating sodium metasilicate as a development accelerating agent which also serves as the alkali source, and thedevelopmenteffectexertedbytheobtaineddevelopingsolution on an inorganic resist, will be described.
The composition of the developing solution of Example 28 and the evaluation method will be shown in the following.
Additive doubling as alkali source: sodium metasilicate
Evaluation: Development, titration
A resist master was obtained by carrying out the resist master production process and exposure process in the same manner as in Comparative Example 1. Subsequently, sodium silicate as a development accelerating agent which doubles as an alkali source was dissolved in pure water, and thus a developing solution at 0.2 mol/L was prepared. Subsequently, development of the inorganic resist master was performed in the same manner as in Comparative Example 1, except that this developing solution was used, and a desired resist master for optical disc was obtained.
Subsequently, the grooves formed on the inorganic resist master were measured by using AFM. The results are presented in Table 5 and Fig. 53.
Furthermore, the developing solution used in the development was titrated with hydrochloric acid, and the relationship between the amount of dropwise addition of hydrochloricacidandthepHaswellas conductivitywasdetermined. The results are presented in Fig. 54. Here, the measurement was carried out by titrating a dilution which was prepared by adding 50 ml of pure water to a 10-ml sample of the developing solution, with 0.5 normal hydrochloric acid.
(Table 5)(Table removed)
In Example 2 9 to Example 42, the method for preparing a developing solution by using a 2.38 wt% aqueous solution of tetramethylammonium hydroxide as an alkaline aqueous solution, and incorporating thereto a development accelerating agent, and the development effect exerted by the obtain eddeveloping solution on an inorganic resist, will be described.
A resist master was obtained by carrying out the resist master production process and exposure process in the same manner as in Comparative Example 1. Subsequently, the development accelerating agents shown in Table 6 were added to a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, and developing solutions at a concentration of 10 g/L were prepared
for the respective development accelerating agents. Subsequently, development of the inorganic resist master was performed in the same manner as in Comparative Example 1, except that these developing solutions were used, and a desired resist master for optical disc was obtained. Subsequently, the grooves formed on the inorganic resist master were measured by using AFM. The results are presented in Table 6 and Fig. 55, Fig. 57, ..., Fig. 65, and Fig. 67.
Furthermore, the developing solutions used in the development were titrated with hydrochloric acid, and the relationship between the amount of dropwise addition of hydrochloricacidandthepHaswellas conductivitywasdetermined. The results are presented in Fig. 56, Fig. 58, ..., Fig. 66, and Fig. 68. Here, the measurement was carried out by titrating a dilution which was prepared by adding 50 ml of pure water to a 10-ml sample of the developing solution, with 0.5 normal hydrochloric acid.
(Table 6) (Table removed)
As shown by the titration curves of Fig. 56, Fig. 58, ..., Fig. 66, and Fig. 68, these alkali metal salts do not have points of neutralization other than the main alkali source. It is thought that the development acceleration due to the addition of these salts is not based on the catalytic action as in the case of the first and second embodiments, but is based only on the accelerating effect of the alkali metal ions.
First, a resist master was obtained by carrying out the resist master production process and exposure process in the same manner as in Comparative Example 1. Subsequently, the development accelerating agents shown in Table 5 were added to a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, and four types of developing solutions at concentrations of 0. 0 g/L, 2.5 g/L, 5 . 0 g/L and 10 . 0 g/L were prepared. Subsequently, development of the inorganic resist master was performed in the same manner as in Comparative Example 1, except that these developing solutions were used, and the time taken until the half-width of the groove width reached 164 nm, was determined. The relationshipbetween the amount of addition of the development accelerating agent and the development time is presented in Fig. 69 and Fig. 70.
(Table 7) (Table removed)
By using the above-des ribed results, the combination of the alkali source and the development accelerating agent can be appropriately selected in accordance with the type of the inorganic resist used or the surface morphology determined after development. For example, in the production of the resist master of a master stamper for optical disc, good pattern shapes can be respectively obtainedby carrying out usage distinction, such as using a product prepared by adding tetramethylammonium metasilicate to an aqueous solution of tetramethylammonium hydroxide as a development accelerating agent when fabricating the groove shape, or using a product prepared by adding tetramethylammonium carbonate to an aqueous solution of tetramethylammonium hydroxide as a development accelerating agent when fabricating the pit shape. Furthermore, stable development properties can be obtained from the time of initiation
of use, as a result of the addition of development accelerating agents.
As discussed above, embodiments and Examples of the present inventionhavebeen described in detail, but the present invention is not intended to the above-described embodiments and Examples, and various modifications based on the technical idea of the present invention are possible.
For example, the numerical values mentioned in the above-described embodiments and Examples are only examples after all, and numerical values different from these may also be used as necessary.
Furthermore, the present invention is also applicable to various optical discs, in addition to Blu-ray Disc (registered trademark), HD-DVD (Heigh Definition Digital Versatile Disc) and the like, and is also applicable to the next generation optical discs of higher density than the conventional optical discs as well as those optical discs such as Blu-ray Disc (registered trademark) or HD-DVD.
In the above-described embodiments andExamples, the cases where the present invention is applied to the method for producing a resist master for optical discs, have been discussed, but the present invention is not intended to be limited to the method for producing a resist master for optical discs, and is applicable to various devices having a fine concavo-convex pattern, for example, the anti-reflective structure in solar cells, the fuel flow channel in fuel cells, and the like, ormethods f orproduction thereof.
In the above-described embodiments and Examples, explanation was given on the case where the present invention was applied to the method for producing of a resist master which is used in the production of substrates for optical discs, but the present invention may also be applied to the method for producing a resist master which is used in the formation of intermediate layers of optical discs.
CLAIMS
1. A developing solution comprising:
an alkaline aqueous solution; and
at least one anion of a silicate ion, a carbonate ion, a borate ion and a phosphate ion.
2. The developing solution according to claim 1, wherein the alkaline aqueous solution is an aqueous solution of tetraalkylammonium hydroxide.
3. The developing solution according to claim 1, further comprising at least one of an ammonium ion and an organic ammonium ion as a cation.
4. The developing solution according to claim 1, further comprising an alkali metal ion as a cation.
5. The developing solution according to claim 1, further comprising an alkali metal ion and at least one of an ammonium ion and an organic ammonium ion, as cations.
6. The developing solution according to claim 1, wherein when the inorganic resist is developed, the anion repeatedly acts on the inorganic resist in the alkaline aqueous solution.
7. The developing solution according to claim 1, wherein when the inorganic resist is developed, the anion forms a bond with the inorganic resist.
8. The developing solution according to claim 1, wherein when titration is performed with an acid to determine a titration curve showing the relationship between the amount of dropwise addition and pH, the point of neutralization of the alkaline aqueous solution and an inflection point originating from the
anion appear on the titration curve.
9. The developing solution according to claim 1, wherein
the pH of the alkaline aqueous solution is set at a value higher
than any of the pH values of the point of neutralization and
the inflection point appearing on the titration curve.
10. The developing solution according to claim 9, wherein when titration is performed with an acid to determine a titration curve showing the relationship between the amount of dropwise addition and conductivity, the titration curve has a minimum region between the point of neutralization of the alkaline aqueous solution and the inflection point originating from the anion.
11. A developing solution comprising an alkaline aqueous solution and a development accelerating agent,
wherein the development accelerating agent is at least one of a silicate, a carbonate, a borate and a phosphate.
12 . The developing solution according to claim 11, wherein the salt is a product produced by a reaction between the alkaline aqueous solution and at least one of silicon, a silicon compound, a carbon compound, a boron compound and a phosphorus compound.
13 . The developing solution according to claim 11, wherein the salt is a product produced by a reaction between at least one selected, as an alkali component, from the group consisting of an alkali metal compound, an ammonium compound and a basic oxide, and at least one selected, as an acid component, from the group consisting of a protonic acid, an acidic oxide, an amphoteric oxide and an amphoteric hydroxide.
14 . The developing solution according to claim 11, wherein
the cation of the alkali source of the alkaline aqueous solution and the cation of the development accelerating agent are the same species.
15 . The developing solution according to claim 14 , wherein the cation of the alkali source of the alkaline aqueous solution and the cation of the development accelerating agent are ammonium ions or organic ammonium ions.
16. A method for producing a finely patterned material,
the method comprising:
exposing an inorganic resist layer provided on a base material; and
developing the exposed inorganic resist with a developing solution,
wherein the developing solution contains:
an alkaline aqueous solution;, and
at least one anion of a silicate ion, a carbonate ion, a borate ion and a phosphate ion.
17. The method for producing a finely patterned material
according to claim 16, further comprising producing a developing
solutionbyaddingasilicate, acarbonate, aborateandaphosphate
to the alkaline aqueous solution, prior to the exposing.