Technical field
[0001]
　The present invention relates to a method of manufacturing a manufacturing method and an electronic device of the flattening film embedded.
Background technique
[0002]
　Electronic device (semiconductor device, a circuit board or the like) in the art, such as, by forming the flattening film embedded with respect to a member having a concave portion, it is possible to flatten an area including the concave portion of the member.
　For example, for isolation trench of the semiconductor substrate (member) having an isolation trench (recess), chemical vapor deposition (CVD) and by the spin coating method, which is an insulating film having a two-layer groove embedded insulating film there is known a method of forming a (buried planarizing film) (e.g., see Japanese Patent Laid-Open No. 11-150179).
Disclosure of the Invention
Problems that the Invention is to Solve
[0003]
　Meanwhile, in the field of semiconductor device miniaturization, year by year, narrowing the gap of the recess (narrowing of the width of the recess) proceeds with miniaturization of the element, the aspect ratio of the recess present in the semiconductor device (depth to width the ratio [depth / width]) tends to increase significantly. Therefore, the planarization layer buried formed by vapor deposition method such as CVD, because only the upper portion of the recess from being closed, tends to filling property (embedding property) is lowered relative to the recess (i.e., the recess it is possible to fill the inside there is a difficult trend) of.
　Therefore, instead of vapor deposition method, a method of forming the planarizing film embedded by the coating method using a coating liquid is considered to be advantageous.
[0004]
　Further, the planarization film embedded is the heat resistance (e.g., resistance to heat treatment that may be performed after embedding planarization film formation) are required.
[0005]
　The present invention has been made in view of the above, and aims to achieve the following objects.
　It is an object of the present invention is excellent in filling property for the recess (embedding property), capable of forming a flattening film buried excellent in heat resistance, it is to provide a method for producing a planarizing film embedded.
　Another object of the present invention is to provide a method of manufacturing an electronic device using the method of manufacturing the buried planarizing film.
Means for Solving the Problems
[0006]
　Specific means for solving the problem includes the following aspects.
<1> in the region including the concave portion of the member having a recess, a first coating step of a first coating solution containing a polyamine and a first solvent is applied to embed the first coating liquid in the concave portion,
　the said member first in a region including the recess 1 coating liquid is embedded, SP value is the organic matter and a boiling point of 200 ° C. or less having at least two carboxyl groups is 30 (MPa) 1/2 second containing the second solvent is less than 2 by applying the coating solution, a second coating step of forming a planarizing film embedded to planarize the region including the concave portion of the member
having a method for producing a planarizing film embedded.
<2> the organic matter having a carboxyl group, a divalent or higher carboxylic acids, method for producing a planarizing film embedded according to <1>.
<3> The content of the polyamine first coating solution is not more than 1.0 mass% to 20 mass% <1> A process for producing a planarizing film embedded according to <2>.
<4> the first solvent, boiling point of 200 ° C. or less, a hydrophilic, <1> to <3> or planarizing film manufacturing method of embedding according to one of.
<5> having the buried planarization film amide bond, <1> to <4> any method for producing a planarizing film embedded according to one of.
<6> the recess has a width is at 250nm or less, is 0.3 or more ratio of the depth [depth / width] to the width, embedding according to any one of <1> to <5> method for producing a planarizing film.
<7> content per unit area of the metal element in the embedding planarization film is a metal element per type, 5 × 10 10 the atom / cm 2Hereinafter is, <1> to <6> any method for producing a planarizing film embedded according to one of.
<8> <1> to the production process of the buried planarizing film according to any one of <7>, to the semiconductor substrate or the circuit board is a member having the recess to form said buried planarization film embedded with a planarizing film forming step, a method for fabricating an electronic device.
<9> further comprises a removing step of removing the buried planarization film, method of manufacturing an electronic device according to <8>.
Effect of the invention
[0007]
　According to the present invention, excellent filling property for the recess (embedding property), capable of forming a flattening film embedded with excellent heat resistance, the production method of the planarization film embedded it is provided.
　Further, according to the present invention, a method for fabricating an electronic device using the manufacturing method of the buried planarizing film is provided.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008]
In [1] Example 1 is a scanning electron microscope showing the cross section of recesses filled with the planarizing film buried (groove) (SEM) photograph (magnification 200,000 ×).
It is a graph showing the results of TOF-SIMS measurement in [2] Experimental Example 9.
In [3] Example 2 is a transmission electron microscope showing the cross section of recesses filled with the planarizing film buried (groove) (TEM) photograph (magnification of 100,000 times).
In [4] Example 3 is a scanning electron microscope showing the cross section of recesses filled with the planarizing film buried (groove) (SEM) photograph (magnification 150,000 ×).
In [5] Embodiment 4 is a scanning electron microscope showing the cross section of recesses filled with the planarizing film buried (groove) (SEM) photograph (magnification 150,000 ×).
In [6] Comparative Example 1 is a scanning electron microscope showing a cross section of the recess (groove) which compares film is formed (SEM) photograph (magnification 150,000 ×).
DESCRIPTION OF THE INVENTION
[0009]
　Hereinafter, embodiments of the present invention (hereinafter, also referred to as "present embodiment") will be described.
　In the present specification, the numerical range expressed using "to" means a range including numerical values described before and after "to" as the lower and upper limits.
　In the present specification, the term "process" not only separate steps, if desired object is achieved in another step and clearly even if indistinguishable the process, the term include.
　Further, in this specification, the term "coating" means a membrane in general obtained by applying the coating solution. The concept of "coating", as well as film state before drying even after application of the coating liquid film state after drying even after application of the coating liquid, and, after application of the coating liquid there are heat treatment (e.g., below a soft bake, a hard bake described later, etc.) film state after also encompassed.
　Further, in this specification, the thickness of the film may be referred to as "film thickness".
　Moreover, SP value in the present specification refers to Hansen solubility parameter, Hansen Solubility Parameter A User's Handbook (Charles M. Hansen al, CRC Press; 1 st Edition) according refers to a value calculated by the following equation.
　= [delta] (([delta] D) 2 + ([delta] P) 2 + (delta] H) 2 ) 1/2
in [wherein, [delta] is SP value (i.e., Hansen parameters) represent, [delta] D represents the dispersion term, the [delta] P represents a polarity term, delta] H represents a hydrogen bond. ]
[0010]
Manufacturing method of embedding planarization film]
　manufacturing method of embedding planarization film of the present embodiment (hereinafter, also referred to as "manufacturing method of this embodiment") is a region including the concave portion of the member having a recess, a polyamine and in a region including a first coating step of filling the first coating liquid in the recess by applying a first coating solution containing a first solvent, the recess in which the first coating liquid is embedded in said member, a carboxyl group organics and boiling with two or more are SP values at 200 ° C. or less 30 (MPa) 1/2 by applying a second coating solution containing a less second solvent is, the area including the concave portion of the member having a second coating step of forming a planarizing film buried to flatten.
　The manufacturing method of this embodiment may have other steps as necessary.
　Other processes include processes known in the semiconductor process or the circuit board process.
[0011]
　In this embodiment, the embedding planarization film refers to film having at least partially embedded in the recess by (i.e., is the filling) that the ability to planarize the area including the concave member having a recess.
　Embedding planarization film may be formed only on the inside of the recess (filled) (e.g., see FIG. 4), formed inside (filling) has been the recess on the external (recess above the recess, and , which may be formed to protrude to the flat portion of the periphery) of the recess (e.g., see FIGS. 1, 3 and 5).
[0012]
　According to the manufacturing method of this embodiment, excellent filling property for the recess (embedding property), it is possible to form an excellent embedding planarization film in heat resistance.
　The reason for this effect is achieved is believed to be as follows.
　That is, in the manufacturing method of the present embodiment, the area including the concave portion of the member having a concave portion, a planarization film embedded by sequentially applying a first coating liquid and second coating liquid.
　In the manufacturing method of the present embodiment,
　the first coating solution, easy to fill the recess easily reach the bottom of the recess (i.e., embedded easily) be liquid, and,
　the second solvent in the second coating solution , solvent hardly dissolving the polyamine filled in the recess (elution) the application of the first coating liquid, i.e. (specifically 30 (MPa) SP value is lower half by the following) as a solvent,
the recess It is considered to be a planarization film buried excellent filling property (embedding property) for.
　Furthermore, in the manufacturing method of this embodiment, in the inside of the recess of the member, with a polyamine of the first coating solution the two or more and an organic substance having reacts (preferably a carboxyl group of the second coating solution, the polyamine amino by the carboxyl group of the group and organic, amide bond, amide imide bond, and at least one imide bonds are formed), it is considered possible to form an excellent embedding planarization film in heat resistance.
　It relates the second coating step, more specifically, SP value in the second coating liquid 30 (MPa) 1/2Because it contains a second solvent or less, in the second coating step, a phenomenon of the polyamine begins to melt in the second coating liquid (second solvent), and, a phenomenon that decreases the packing against the recess by such phenomena It is suppressed. Therefore, in the second coating step, easily penetrate the organic material having two or more carboxyl groups to the bottom of the recess, penetrate the organic matter reacts well polyamines and efficiency that are present inside the recess. Therefore, excellent filling property for the recess, and is considered that it is possible to form an excellent embedding planarization film in heat resistance.
　For the above reasons, according to the manufacturing method of this embodiment, excellent filling property for the recess (filling property), it is considered possible to form a good embedding planarization film in heat resistance.
[0013]
　As described above, the present embodiment, the polyamine is SP value 30 (MPa) 1/2 has been made in view of the points easily dissolved in excess of the solvent (e.g. water), into the recess due to the dissolution of the polyamine has been accomplished as a means for suppressing the deterioration of the filling property.
　Further, the present embodiment is found that films having excellent heat resistance by reaction with organic material having a polyamine and a carboxyl group two or more can be obtained, has been completed.
[0014]
　The manufacturing method of this embodiment, since the boiling point of the second solvent is at 200 ° C. or less, the advantage that hardly remains in the planarization film the second solvent is embedded (e.g., easily be removed from within the coating by evaporation) also it has.
[0015]
　Further, planarization layer buried manufactured by the manufacturing method of this embodiment, as described above, polyamines and was film (preferably an amide obtained by reaction with organic material having a carboxyl group of the second coating liquid in the two or more because a membrane) with binding, resistance to plasma that may be irradiated after implantation flattening film formation (hereinafter, also excellent also referred) to as "plasma resistance".
　The plasma referred to herein, helium gas, argon gas, nitrogen gas, ammonia gas, and plasma generated from at least one gas selected from the group consisting of fluorocarbon-based gas and the like.
[0016]
　Meanwhile, as the excellent film in heat resistance, polyimide films have been widely known.
　However, the study by the present inventors, the polyimide film tends to shrink after application, Therefore, in the case of using the polyimide film as a planarizing film embedding packing against recesses clear that there is a tendency to decrease became. Further, in the case of using the polyimide film as a planarizing film buried, because the pattern shift occurs by the contraction, increasing the design dimension margin inevitably. Therefore, it becomes difficult narrower pitch design of electronic devices (semiconductor devices, etc.).
　For these problems, according to the manufacturing method of this embodiment, embedded in comparison with a method of forming a polyimide film as a planarizing film, a planarization film buried excellent filling property for the recess. Therefore, it is possible to reduce the design dimensions margin, it is facilitated narrower pitch design of electronic devices (semiconductor devices, etc.).
[0017]
　In the production method of the present embodiment, the organic substance having a carboxyl group contained in the second coating solution is more than one, preferably a divalent or higher carboxylic acids. Thus, the heat resistance of the planarizing film embedded is further improved. When organic material having a carboxyl group two or more is a divalent or higher carboxylic acids, can be the upper temperature limit of the flattening film embedded, for example, 350 ° C. or higher. When organic material having a carboxyl group two or more is a divalent or higher carboxylic acids, also further improved plasma resistance of the buried planarization film.
[0018]
　From the viewpoint of further heat resistance of the planarizing film buried improved, organic matter having a carboxyl group contained in the second coating solution is more than one, is preferably a trivalent or higher carboxylic acids. When organic material having a carboxyl group two or more is a trivalent or higher carboxylic acids, can be the upper temperature limit of the flattening film embedded, for example, 400 ° C. or higher.
　Further, when the organic substance having two or more carboxyl groups is a trivalent or higher carboxylic acids, also further improved plasma resistance of the buried planarization film. When organic material having a carboxyl group two or more is a trivalent or higher carboxylic acids, for example, helium gas, argon gas, nitrogen gas, ammonia gas, and at least one gas selected from the group consisting of fluorocarbon gas the etching rate of the planarizing film buried for resulting plasma, SiO against the plasma 2 can be suppressed to the film etching rate equal to or less.
[0019]
　In the production method of the present embodiment, the first solvent, boiling point of 200 ° C. or less, preferably a hydrophilic solvent.
　By boiling point of the first solvent is 200 ° C. or less, hardly remaining in the planarization film the first solvent is embedded (e.g., easily be removed from within the coating by evaporation) effects are achieved that.
　The first solvent If it is hydrophilic, the solubility of the polyamine to the first solvent is further improved, and thus the stability of the first coating liquid is further improved.
[0020]
　In the production method of the present embodiment, embedding planarization film preferably has an amide bond. By having an amide bond, ultimately it is possible to crosslink the polyamine in three dimensions. Thus, the heat resistance of the planarizing film embedded is further improved.
　If having a planarizing film embedded amide bond, embedding planarization film, in addition to the amide bond may have at least one of the imide bonds and amide imide bond.
[0021]
　In the production method of the present embodiment, the recess has a width of 250nm or less (preferably 200nm or less, more preferably 100nm or less), and the ratio of depth to width [depth / width] (hereinafter "aspect ratio" also referred) is preferably embodiment is 0.3 or more (preferably 0.5 or higher).
[0022]
　Recess of the above aspects (short, narrow width, the recess having a large aspect ratio) is, generally speaking, a recess tends it is difficult to embed a planarization film embedded.
　However, in the manufacturing method of this embodiment, since a planarization film embedded with a liquid (first coating liquid and second coating liquid), also to the recess of the above embodiments, the filling property (embedding property) it is possible to form the excellent embedding planarization film.
　In other words, in the case of forming a planarizing film embedded with respect to the concave portion of the above embodiment, the effect of the filling property of the present embodiment (filling property) is particularly effectively exhibited.
[0023]
　In the production method of the present embodiment, the heat resistance temperature of the planarizing film embedded, from the viewpoint of heat resistance, it is preferably 350 ° C. or higher.
[0024]
　In this specification, a heat resistance temperature, the thickness of the film subjected to heat treatment for 30 minutes with respect to the film thickness of the film subjected to heat treatment for 10 minutes (the following formula (1) represented by "30 minutes heat treatment after film remaining ratio") is, refers to the temperature of heat treatment is 30% or more.
[0025]
　30 minutes heat treatment after film remaining ratio (%) = (30 min heat-treated film having a film thickness of / 10 min heat treated film thickness of) × 100 ... formula (1)
[0026]
　The film thickness of the buried planarizing film can be measured by observing the cross section of the recess. Embedding planarization film material itself of the heat-resistant or residual film ratio, or, in order to assess whether it is film formation, forming a film in the first coating step and the second coating step using a flat substrate then, it may be to measure the film thickness. In the case of using a flat substrate, it can be measured using an ellipsometer.
[0027]
　Further, in the manufacturing method of this embodiment, the embedding planarization film, from the viewpoint of heat resistance, it is preferred that the void does not occur when heated at 350 ° C. over 30 minutes.
　Here, the void and refers to voids (i.e., a planarization film embedded is not filled in the recess gap portion) in the planarization film buried buried in the recess.
[0028]
　In the production method of the present embodiment, from the viewpoint of bringing Criteria to semiconductor process steps, the content per unit area of the metal element in the embedded planarization film is a metal element per type, 5 × 10 10 the atom / cm 2 is preferably not more than.
　Here, "content per unit area of the metal elements in the embedding planarization film is a metal element per type, 5 × 10 10 the atom / cm 2 in the range of equal to or less than" aspects of the embedded planarization film,
　planarization layer embedding the metal element not included one kind,
　the metal element is included only one type, and the content of the metal element × 10 5 10 the atom / cm 2 or less is embedded planarizing film and,
　contains metal elements are two or more and the content of each 5 × 10 of each metal element 10 the atom / cm 2 or less is embedded planarization layer (e.g., the content of Fe 5 × 10 10 the atom / cm 2 , and the content of Cu is 5 × 10 10 the atom / cm 2 is the content of Al is 5 × 10 10 the atom / cm 2 is, the Sn content of 5 × 1010 the atom / cm 2 is, the Ti content × 10 5 10 the atom / cm 2 embedded planarizing film) is
includes all.
　Metal element content of the embedded planarization film surface is measured by total reflection X-ray fluorescence (Total Reflection X-ray Fluorescence) analysis (TXRF). The metal content measurement, usually using a total reflection X-ray fluorescence. The metal content measurement, is to measure the one provided a planarizing film embedded member having a recess, other, using a film formed on a planar substrate such as a silicon wafer, it is measured metal content good.
[0029]
　Content per unit area of the metal element in the embedded planarizing film is, metal elements one per × 10 5 10 the atom / cm 2 embedded planarization film embodiments or less is removed by UV ozone treatment or plasma treatment that film (i.e., the sacrificial layer) is particularly suitable as a. This is because, when the sacrificial layer is removed, there is a possibility that the residual contamination because metallic elements in the UV-ozone treatment or plasma treatment.
[0030]
　Planarization film embedded in this embodiment, may be only formed (filled) in the interior of the recess formed in the recess of the concave portion on which is (filled) outside (upper recesses, and the recesses of surrounding or may be formed to protrude to the flat portion).
　If planarization film buried is formed protrudes to the outside of the recess, the recess of the outer (upper recess, and a flat portion around the recess) particular limitations on the upper limit of the thickness of the planarization layer buried in without this limit, for example 100nm and it is possible to, 50 nm are preferred, 10 nm is more preferable.
[0031]
　The following describes each step of the manufacturing method of this embodiment.
[0032]

　The first coating step, the region including the concave portion of the member having a recess, the step of the first coating liquid containing a polyamine and a first solvent is applied filling the first coating liquid to the recess it is.
　The first coating step, in addition to the coating step of coating a first coating liquid, drying step for drying the first coating liquid coated, heat treatment steps, including such a heat treatment a first coating solution applied It can have.
[0033]
(Member having a concave portion)
　member having a concave portion is a member to be formed in the planarizing film embedded.
　The "member" in the member having a concave portion, the semiconductor substrate (or semiconductor device) such as a silicon wafer, a circuit board (e.g. printed circuit board), and the like.
　The recess may be a groove (e.g. trenches) may be holes (e.g., vias).
　As the recess, more specifically,
the concave portion (e.g., isolation trench, via, etc.) formed by etching to members,
a plurality of conductive portions provided on the member (e.g., a metal electrode or wiring, such as Cu) and the side surface of the recess to be determined and the surface of the member, by,
and the like.
　A preferred range of the width and the aspect ratio of the recess is as described above.
[0034]
(First coating liquid)
　first coating liquid is a liquid containing a polyamine and a first solvent.
　PH of the first coating solution (25 ° C.) is preferably 4.0 to 11.0 and more preferably from 6.0 to 11.0 more preferably 6.0-9.0.
[0035]
- first solvent -
　There is no particular limitation on the first solvent contained in the first coating solution may be a mixed solvent may be a single solvent. The first solvent is preferably a different solvent than the second solvent.
　As the first solvent, as described above, boiling point of 200 ° C. or less, it is preferable that the solvent is hydrophilic.
　As the first solvent, water, a boiling point of 200 ° C. or less of the water-soluble organic solvent (alcohols such as methanol, ethanol, etc.), and the like.
[0036]
　If the boiling point of the first solvent is at 200 ° C. or less, as described above, the first solvent is less likely to remain in the planarizing film embedded. For example, the first solvent is easily evaporated removed from the coating during the first coating step (e.g. in rotation by a spin coater).
　The boiling point of the first solvent is preferably from 50 ° C. ~ 200 ° C., more preferably from 60 ℃ ~ 140 ℃.
　By boiling point of the first solvent is 50 ° C. or more, excellent handling properties of the first coating liquid. For example, in the case of using the coating apparatus comprising a nozzle (e.g., a spin coater), the nozzle clogging can be suppressed.
[0037]
　By first solvent is hydrophilic, as described above, to improve the solubility of the polyamine, the stability of the first coating solution is improved.
　Therefore, it is preferable that the first solvent is a hydrophilic solvent.
　Here, the hydrophilic solvent refers to SP value is high solvent.
　More specifically, SP value of the first solvent, 24 (MPa) 1/2 is preferably at least, 26 (MPa) 1/2 , more preferably at least, 30 (MPa) 1/2 further preferably super.
　There is no particular restriction on the upper limit of the SP value of the first solvent, the upper limit, e.g., 50 (MPa) 1/2 include.
　When the first solvent is a mixed solvent comprising plural solvents species, SP value of the first solvent, based on the SP values and molar fraction of each solvent species, determined by proportional distribution calculation (RFFedors Polym.Eng.Sci ., 14,147 (1974)).
[0038]
　As the first solvent, water (at least one preferably methanol or ethanol) alcohol, or water and alcohol (preferably at least one of methanol or ethanol) mixed solvent of is preferred.
　The first solvent preferably comprises water.
[0039]
- polyamine -
　contained in the first coating liquid, a polyamine, it refers to an aliphatic hydrocarbon compound having two or more amino groups (preferably a polymer compound).
[0040]
　It is not particularly limited in molecular weight of the polyamine, the weight average molecular weight of the polyamine, it 2,000 to 1,000,000 are preferred, more preferably 2,000 to 600,000 more preferably from 10,000 to 200,000, 20,000 to 200,000 but more preferably, it is more preferably from 20,000 to 150,000.
[0041]
　In this specification, weight average molecular weight and molecular weight distribution, it refers measured by GPC (Gel Permeation Chromatography) method, a weight average molecular weight and molecular weight distribution of the polyethylene glycol conversion.
　The weight average molecular weight and molecular weight distribution, measured using the acetic acid concentration 0.5 mol / L, an aqueous solution of sodium nitrate concentration 0.1 mol / L, analyzer Shodex GPC-101 and column Asahipak GF-7M HQ as a developing solvent It is calculated polyethylene glycol as a standard.
[0042]
　Moreover, polyamines, amino group preferably contains a repeating unit structure having at least one quaternary ammonium group and imino group.
　If the polyamine includes a repeating unit structure above, the repeating unit structure contained in the polyamine, it may be two or more be only one.
　It said repeating unit structure is preferably a molecular weight of 30-500.
　If the polyamine includes a repeating unit structure above, the total content of amino group, quaternary ammonium group and imino group, is preferably a weight average molecular weight per 10-2500 polyamine.
　Needless to say, the term "amino group, quaternary ammonium groups, and imino total content of group", polyamine, a "repeating unit structure having no quaternary ammonium group and imino group having an amino group" when it contains refers to the content of the amino group.
[0043]
　The polyamines,
polyalkyleneimines (e.g., polyalkylene imine having 2 to 12 carbon atoms (preferably a polymer of an alkylene imine having 2 to 8 carbon atoms, more preferably 2 to 4 carbon atoms), particularly preferably polyethyleneimines (PEI)),
polyallylamine (PAA),
polydiallyldimethylammonium (PDDA),
polylysine,
can be cited, and these derivatives.
　Among them, preferably,
polyalkyleneimine (e.g., C 2-12 (preferably having 2 to 8 carbon atoms carbon atoms, more preferably a polyalkylene imine or a derivative thereof is a polymer of an alkylene imine having 2 to 4) carbon atoms,
　particularly preferably,
polyethylene imine (PEI)) or a derivative thereof.
[0044]
　The polyamines
　are described in WO 2010/137711, "weight average molecular weight from 2,000 to 100,000 resin having two or more cationic functional groups",
　are described in WO 2013/108791, " tertiary nitrogen atom and a quaternary nitrogen atom polymer more weight average molecular weight has a cationic functional group is 2,000 to 1,000,000 branching degree including at least one is not less than 48% ", and
　WO 2014 / "polymer weight average molecular weight has a cationic functional group is 2,000 to 1,000,000" described in JP 013 956
from among may be used in selecting what corresponds to the polyamine.
[0045]
　The first coating liquid, polyamine to which may contain only one kind, may contain two or more kinds.
　The first amount of the polyamine in the coating liquid (the total content in the case where two or more. Hereinafter the same.) Is not particularly limited to, can form a thicker coating, filling of the recess in that further improved with respect to the first coating liquid total amount, preferably 1.0 mass% or more, still more preferably 1.5 mass% or more, further to be 2.0 mass% or more preferable.
　There is no particular limitation on the upper limit of the content of the polyamine in the first coating solution. However, from the viewpoint of further improving the filling of the interior of the recess by reducing the viscosity of the first coating liquid, the content of the polyamine in the first coating solution is for the first coating liquid total amount, e.g. It can be 20 mass% or less, preferably 15 wt% or less, more preferably 10 wt% or less.
[0046]
　The first coating liquid may contain other components other than the polyamines and the first solvent.
　As the other components that may be included in the first coating liquid, the compound having a boiling point of 210 ° C. or less (preferably 160 ° C. or less), and, the group consisting of be heat-treated to 250 ° C. without a decomposable compound it is preferably at least one selected from.
　Incidentally, the "be heat-treated to 250 ° C. without decomposition compound" for the mass measured at 25 ° C., 250 ° C., the change in mass after 1 hour under nitrogen is less than 50% It refers to a compound.
　Further, in the first coating solution, for the purpose of pH adjustment, or by adding an acid. However, acid tend to aggregate or insolubilize a crosslinking reaction of a polyamine, such as a di- or higher-valent acid (i.e., acids having a crosslinking point) is not suitable.
　On the other hand, formic acid, acetic acid, monocarboxylic acid compounds such as benzoic acid is suitable acid. In particular, a monovalent aromatic carboxylic acids having small molecular weight, both amines divalent or higher carboxylic acid is in the site where hardly react attached, can be reduced unbound amine, can be reduced and the water adsorption, and thus the film properties can be improved is expected.
[0047]
(First of the coating method)
　The method for applying the first coating solution is not particularly limited, it is possible to use a generally used method.
　As a coating method such as spin coating, slit coating method, a dipping method, a spray method, etc., and spin coating it is particularly preferred. Coated by the spin coating method can be carried out using a spin coater as a coating apparatus.
[0048]
(Coating of the first coating liquid)
　it is not particularly limited in thickness (coating thickness) of the coating film of the first coating solution, fit the depth of the recess, the thickness of the recess is filled preferably, for example, 20 nm ~ 1000 nm is preferable.
[0049]
　In the first coating step, in the case of performing the heat treatment to be described later (e.g., soft bake), the film thickness before the heat treatment, it is preferable to thicken in anticipation of the volume contraction of the heat treatment.
　The film thickness of the pre-heat treatment depends on the depth of the recess, 100 nm ~ 1000 nm is preferable.
[0050]
(Heat treatment)
　first coating step, in addition to the coating step of coating a first coating liquid may contain a heat treatment step of heat treating the first coating solution coated on the member.
　By including the first coating step is a heat treatment step, in the second coating step, in the second coating solution can further reduce the polyamine is dissolved, easily to more residual polyamines in the interior of the recess.
[0051]
　The heat treatment in the heat treatment step, the member first coating liquid has been applied, a process of heating under the conditions of less than 200 ° C. temperature of 70 ° C. or more and it is preferable that a (hereinafter, also referred to as "soft bake").
　By temperature is 70 ° C. or higher, the second coating step, the polyamine in the interior of the recess is more easily remain. Moreover, evaporative removal of the first solvent from the coating film of the first coating liquid is also improved.
　Further, when the temperature is lower than 200 ° C., it is possible to perform the subsequent cooling of the member more quickly, it is possible to perform the next step (a second coating step) more quickly.
　The above temperature is more preferably from 85 ° C. ~ 0.99 ° C., more preferably 90 ℃ ~ 125 ℃.
　Note that the temperature of the heat treatment is low, the device heat treatment, it is also advantageous in that it can be used a simple device such as a hot plate.
[0052]
　The atmosphere in which heat treatment (e.g., soft bake) is not particularly limited, for example, may be a air atmosphere, an inert gas (nitrogen gas, argon gas, helium gas, etc.) may be atmosphere.
[0053]
　There is no particular restriction on the time of heat treatment (e.g., soft bake), preferably 300 seconds or less, more preferably 200 seconds or less, more preferably 120 seconds or less, particularly preferably 80 seconds or less.
　There is no particular limitation on the lower limit of the heating time, the lower limit is, for example, 10 seconds (preferably 20 seconds, more preferably 30 seconds) can be.
[0054]

　The second coating step, a region including the recess the first coating liquid is embedded in said member, organic matter and boiling having two or more carboxyl groups is at 200 ° C. or less SP value 30 (MPa) 1/2 by applying a second coating solution containing a less second solvent which is a step of forming a planarizing film embedded to planarize the region including the concave portion of the member.
　Preferred properties of the planarizing film buried is formed (heat-resistant temperature, the content of metal elements, thickness, etc.) it is as described above.
　In this case, preferably, the amino groups of the polyamine in the first coating solution, the carboxyl groups of the organic substance having a carboxyl group of the second coating solution two or more, the reaction to amide bond, amide imide bond, and imide bond at least one is formed of an amide bond, amide imide bond, and a planarization film embedded with at least one imide bonds are formed.
[0055]
　The method of applying the second coating solution is not particularly limited, it is possible to use a generally used method. As a method for applying the second coating solution, it exemplified a procedure similar to the method for applying the first coating solution (e.g., a spin coating method).
[0056]
　Also, the second coating step as in the first coating step, in addition to the coating step of applying the second coating solution, drying step of drying the second coating liquid coated, heat treated a second coating solution applied heat treatment step of, etc. may be included.
[0057]
(Second coating liquid)
　second coating solution, and organic matter having two or more carboxyl groups, SP value and a boiling point of 200 ° C. or less 30 (MPa) 1/2 includes second solvent or less, and.
[0058]
- second solvent -
　second solvent, SP value and a boiling point of 200 ° C. or less 30 (MPa) 1/2 as a solvent or less.
　The second solvent may be a mixed solvent may be a single solvent.
　By boiling point of the second solvent is 200 ° C. or less, as described above, the second solvent is less likely to remain in the planarizing film embedded. If the boiling point of the second solvent is at 200 ° C. or less, for example, the second solvent is readily evaporated removed from the coating in the second coating step (e.g. in rotation by a spin coater).
　Boiling point of the second solvent is preferably from 50 ° C. ~ 200 ° C., more preferably from 60 ℃ ~ 140 ℃.
　By boiling point of the second solvent is 50 ° C. or more, excellent handling property of the second coating solution. For example, in the case of using the coating apparatus comprising a nozzle (e.g., a spin coater), the nozzle clogging can be suppressed.
[0059]
　Moreover, SP value of the second solvent, 30 (MPa) 1/2 or less.
　Thus, during the second coating step, the polyamine is present in the interior of the recess, the phenomenon that dissolves into the second solvent is suppressed. Therefore, SP value of the second solvent is 30 (MPa) 1/2 by or less, the filling of the recess of the planarization film embedded is improved.
　SP value of the second solvent, above as 30 (MPa) 1/2 but less, and further suppress the dissolution of the polyamine, from the viewpoint of further improving the filling of the recess of the planarization film buried, 24 ( MPa) 1/2 or less is more preferable.
　There is no particular limitation on the lower limit of the 2 SP value of the solvent, as a lower limit, for example, 15 (MPa) 1/2 include.
[0060]
　As the second solvent, cyclohexane, propylene glycol monomethyl ether acetate (PGMEA), toluene, cyclopentanone, dimethylacetamide (DMAc), 2-butanol (2-BtOH), 1-butanol (1-BtOH, isopropyl alcohol (IPA ), dimethylformamide (DMF), 1-propanol (1-PrOH), ethanol (EtOH), methanol (MeOH), and the like.
　in Table 3 below, each for these solvents, the boiling point (bp), log (Pow), and showed a SP value.
[0061]
　The second solvent is preferably the solubility of the organic substance having two or more carboxyl groups is highly solvent. Thus, the stability of the second coating solution is improved.
　A carboxyl group as the high solubility of the organic substance having two or more second solvent, and more specifically, octanol / water partition coefficient log (Pow) is preferably 1.0 or less of the solvent, log (Pow) 0.6 the following solvents are more preferable.
[0062]
　As the second solvent, SP value 24 (MPa) 1/2 or less, a boiling point of 60 ° C. ~ 140 ° C., the solvent log (Pow) is 0.6 or less is particularly preferred.
[0063]
　As the second solvent, the boiling point, SP value, and in terms of log (Pow), propylene glycol monomethyl ether acetate (PGMEA), cyclopentanone, dimethylacetamide (DMAc), isopropyl alcohol (IPA), dimethylformamide (DMF) , 1-propanol (1-PrOH), ethanol (EtOH) are more preferred, cyclopentanone, isopropyl alcohol (IPA), 1-propanol (1-PrOH), or ethanol (EtOH) is especially preferred.
　The second solvent is a mixed solvent consisting of a plurality of solvent species, SP value of the second solvent, based on the SP values and molar fraction of each solvent species, determined by proportional distribution calculation.
　The second solvent is a mixed solvent consisting of a plurality of solvent species, a second solvent of log (Pow) is based on the solvent species of log (Pow) and mole fraction, determined by proportional distribution calculation.
[0064]
- organics having a carboxyl group at least two -
　second coating liquid containing an organic substance having two or more carboxyl groups.
　A carboxyl group as an organic substance having two or more, preferably a carboxylic acid.
[0065]
　The carboxylic acid,
oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, maleic acid, fumaric acid, phthalic acid, isophthalic acid, a dicarboxylic acid such as terephthalic acid;
1,2,3 - propane tricarboxylic acid, trimesic acid, trimellitic acid, tri Kalbarri acrylic acid, trivalent carboxylic acids such as citric acid;
pyromellitic acid, ethylenediaminetetraacetic acid, naphthalene tetracarboxylic acid, biphenyl tetracarboxylic acid, benzophenone tetracarboxylic acid, bicyclo [2.2.2] oct-7-ene-2,3,5,6-tetracarboxylic acid, meso-4-valent carboxylic acid such as butane-1,2,3,4-tetracarboxylic acid);
benzenehexacarboxylic acid, 6 dicarboxylic acids such as cyclohexanehexacarboxylic acid;
hydroxybutyrate, lactate, salicylate ; Oxymonocarboxylic acids such as acid
malic acid, oxy dicarboxylic acid or tartaric acid; oxy tricarboxylic acids such as citric acid
aspartic acid, amino acids glutamic acid;
and the like.
[0066]
　Although there is no particular limitation in the molecular weight of the organic substance having two or more carboxyl groups, as a molecular weight, eg, 90 through 1000 include, preferably 90 to 342, more preferably from 90 to 210. FIG.
[0067]
　The organics having a carboxyl group two or more, as described above, in view of heat resistance and plasma resistance of the flattening film embedded, is preferably a divalent or higher carboxylic acids.
　Here, the concept of divalent or more carboxylic acids, at least some of the plurality of carboxyl groups is obtained by dehydration (e.g. phthalic anhydride) are also included.
　The organics having a carboxyl group two or more, from the viewpoint of further improving the heat resistance and plasma resistance of the flattening film embedded, is preferably a trivalent or higher carboxylic acids.
　No particular limitation is imposed on the valence of the upper limit of the carboxylic acid, from the viewpoint of removability in removing planarization film embedded, the valence of the carboxylic acid is preferably hexavalent or less, tetravalent or less It is more preferable.
[0068]
　The second coating solution, the organic matter having two or more carboxyl groups, may contain only one kind, may contain two or more kinds.
　The second content of the organic substance having two or more carboxyl groups in the coating liquid (the total content in the case where two or more. Hereinafter the same.) Is not particularly limited to, heat resistant planarization film buried from the viewpoint of further improving the, for the second coating liquid total amount, preferably at least 0.5 wt%, and more preferably 1.0 mass% or more.
　There is no particular limitation on the upper limit of the organic material having at least two carboxyl groups in the second coating solution, the content is, for the second coating liquid total amount, for example, it can be 10 mass% or less, 5.0 mass% or less.
[0069]
　The second coating solution may contain other components other than the organic substance having a second solvent and a carboxyl group of two or more.
　As the other components that may be included in the second coating solution, the compound having a boiling point of 210 ° C. or less (preferably 160 ° C. or less), and, the group consisting of be heat-treated to 250 ° C. without a decomposable compound it is preferably at least one selected from.
[0070]
(Heat treatment)
　The second coating step, in addition to the coating step of coating a second coating liquid, the second coating solution may contain a heat treatment step of heating the member coated.
　By the second coating step comprises a heat treatment step, the polyamine and a carboxyl group can more effectively form an amide bond by reaction with organic material having two or more, and thus, further improve the heat resistance of the planarizing film buried be able to.
[0071]
　The heat treatment in the heat treatment step, the member the second coating solution is coated, the process of heating at a temperature of 200 ° C. ~ 425 ° C. It is preferable that a (hereinafter, also referred to as "hard bake").
　By the temperature of the heat treatment is 200 ° C. or higher, amide bond, amide imide bond, and can more effectively form at least one imide bonds, it is possible to further improve the heat resistance of the planarizing film embedded.
　When the temperature of the heat treatment is at 425 ° C. or less, the heat treatment becomes easier. For example, heat treatment can be performed using a more simple device. Furthermore, members having recesses, copper (Cu) member including a metal such as (e.g., wiring, electrodes) when provided with, when temperature is 425 ° C. or less, can be suppressed migration member comprises a metal.
　The temperature of the heat treatment is preferably 250 ° C. ~ 400 ° C., more preferably from 300 ℃ ~ 400 ℃.
[0072]
　No particular limitation is imposed on the pressure of the atmosphere in which the heat treatment is performed, preferably less than or equal to the absolute pressure 17Pa superatmospheric pressure.
　Absolute pressure, more preferably less than atmospheric pressure 1000 Pa, more preferably less than atmospheric pressure 5000 Pa, and particularly preferably more than 10000Pa atmospheric pressure.
[0073]
　The heat treatment can be carried out by conventional methods using a furnace or a hot plate. The furnace, for example, can be used Tokyo and Electron Ltd. of ACT12SOD, and SPX-1120 manufactured by Apex Corporation, the Koyo VF-1000LP made of Thermo System Co., Ltd..
　The heat treatment may be performed in an air atmosphere, an inert gas (nitrogen gas, argon gas, helium gas, etc.) may be carried out in an atmosphere.
[0074]
　No particular limitation is imposed on the time of the heat treatment, for example, not more than 1 hour, preferably 30 minutes, more preferably at most 10 minutes. No particular lower limit to the time for heat treatment is, for example, be a between 0.1 minutes.
[0075]
　In the second coating step, a heat treatment may be carried out both soft bake and hard bake.
[0076]

　As Experimental Example 1 were carried out and the type of organic material having at least two carboxyl groups in the second coating solution, and heat resistance of the coating film, the experiments on the relationship (Table 1).
[0077]
(First coating step)
　as a first coating liquid, polyethylene imine (PEI) coating solution (polyethyleneimine (brand: Rupasol WF (BASF), weight average molecular weight of PEI (Mw): 25000), the first solvent: water , PEI content: 4 wt%, pH = 10.5) was prepared. PEI was used after removing the metal and halogen.
　A flat silicon wafer substrate surface placed on the spin coater (ABLE Co., Ltd. Ltd.), was 1mL discharging a first coating solution using a pipette, then rotates for one second at a rotational speed 1000 rpm, further rotational speed 600rpm in rotated 60 seconds to obtain a dry coating film. The resulting dried coating, on a hot plate (Apex Co. SPX-1120), in air, and soft-baked for 1 minute at 100 ° C., to obtain a coating film (after the soft-bake).
[0078]
(Second coating step)
　for the organic material having at least two carboxyl groups in the second coating solution was prepared of terephthalic acid (Aldrich Corp. 98%) and phthalic acid (Aldrich Co. 99.9%). As the carboxylic acid for comparison was prepared acetic acid (Aldrich Co. 99.7%) a monovalent carboxylic acid. As the second solvent, isopropyl alcohol; was prepared (IPA Wako Junyaku Co. SC grade). Using these, as the second coating solution, terephthalic acid coating solution (terephthalic acid concentration: 0.1 wt%), phthalic acid coating solution (phthalic acid concentration: 2 mass%), and acetic acid coating solution (acetic acid concentration: 3 mass %) were prepared, respectively. Here, acetic acid coating solution is a second coating liquid for comparison.
　On the coating film obtained in the first coating step (after the soft baking), the second coating liquid ejected 1 mL, rotated for 1 second at a rotation speed 1000rpm with a spin coater, rotated further 60 seconds at a rotation speed of 600rpm coating was obtained film (after the second coating liquid coated). The obtained coating film (after the second coating liquid coated), obtained using a hot plate in a nitrogen performs hard bake for 10 minutes at a pressure 30 kPa, 350 ° C., the coating film (hard bake 10 minutes after) It was. The obtained coating film (hard baked 10 minutes later), further, in nitrogen, at a pressure 30 kPa, 350 ° C., was hard baked for 20 minutes (30 minutes in total from the hard bake start).
　In the course of the subsequent hard-baking the start of the above, after 10 minutes from the hard-baked start (hereinafter, also referred to as "hard bake 10 minutes after") coating film having a thickness of, 20 minutes after the hard baking the start (hereinafter, a "hard bake thick coating film also referred to) and after 20 minutes ", and 30 minutes after the hard baking the start (hereinafter, the thickness of the coating film" also referred to as a hard bake 30 minutes after ") were measured.
　Furthermore, based on the thickness of the coating film after film thickness and a hard bake 30 minutes of the coating film after the hard bake 10 minutes, the formula (1) described above, was determined after 30 minutes heat treatment residual film ratio (%). Here, the thickness of the hard bake 10 minutes after the coating as a "film thickness of the heat-treated film 10 minutes" in the formula (1), the thickness of the coating film of a hard bake 30 minutes after the formula (1) " and the thickness of the heat-treated film for 30 minutes. "
[0079]
　The thickness of the coating film was measured by a conventional method using an ellipsometer of SEMILAB manufactured optical porosimeter (PS-1100).
[0080]
　For coating made above, the film obtained by using terephthalic acid coating solution is m film, a film obtained by using the phthalic acid coating solution and n film as a second coating liquid as the second coating solution acetate coating solution as the second coating liquid film obtained by using the (second coating liquid for comparison) and o film, the film not subjected to the second step after the first step is p film.
　The measurement results of the film thickness and 30 minutes heat treatment after film remaining ratio for these films are shown in Table 1 below.
[0081]
[Table 1]

[0082]
　As shown in Table 1, dicarboxylic acid (terephthalic acid, phthalic acid) as the carboxylic acid of the second coating solution m film and n film using, both, after the 350 ° C. heating (hard bake) film is left, after 30 minutes heat treatment residual film rate is 30% or more was found to have a heat resistance of 350 ° C.. On the other hand, o film using monovalent carboxylic acid (acetic acid) (acid for comparison) as a carboxylic acid of the second coating solution, and, p film not using the second coating solution, the 350 ° C. heat It was found to have no sex.
　In this manner, by using the dicarboxylic acid as the carboxylic acid of the second coating solution, it can be seen that the membrane having a heat resistance of 350 ° C. is obtained.
[0083]

　As an experimental example 2 was measured of the metal element content in the coating film (Table 2).
　The metal element content was measured by the total reflection X-ray fluorescence measurement device (Rigaku TXRF300).
　As measurement samples, we were prepared following samples (q membrane).
[0084]
(First coating step)
　as a first coating liquid, polyethylene imine (PEI) coating solution (weight average molecular weight of PEI: 25000), the first solvent: water, PEI content: 4 wt%) was prepared. PEI was used after removing the metal and halogen.
　A flat silicon wafer substrate ([phi] 300 mm) surface placed on the spin coater, after 1mL discharging a first coating solution using a pipette, then rotates for one second at a rotational speed 1000 rpm, rotated further 60 seconds at a rotation speed of 600rpm to obtain a dried coating Te. The resulting dried coating, on a hot plate (Apex Co. SPX-1120), in air, and soft-baked for 1 minute at 125 ° C., to obtain a coating film (after the soft-bake).
[0085]
(Second coating step)
　As the second coating liquid, trimesic acid coating solution (second solvent: isopropyl alcohol (IPA), trimesic acid content: 1.5 wt%) was prepared.
　On the coating film obtained in the second coating step (softbaked), discharged 10mL the second coating solution was rotated for 1 second was applied by a spin coater, rotated further 60 seconds at a rotation speed of 600rpm by coating to obtain a membrane (after the second coating liquid coated). The obtained coating film (after the second coating liquid coated), using a hot plate, subjected to hard baking 10 minutes at 250 ° C., to obtain a coating film (hard baked 10 minutes later). The resulting coating film (hard baked 10 minutes later), further to give the q film was heated for 10 minutes at 400 ° C. under nitrogen.
　Thickness of the obtained q film was measured, was 138.7Nm.
[0086]
　Metal content of the obtained q membrane was measured under the following conditions.
X-ray: 30 kV, 300 mA
wafer in the measuring points: 5Point
Beam:
　W-M ... Fai0.400Deg, measurement time 500 sec, the measuring direction
　35 deg W-Lb ... Fai0.100Deg, measurement time 500 sec, the measuring direction 35 deg
　H. E. ... Φ0.050deg, measurement time 500sec, measurement direction 35deg
[0087]
　The measurement results are shown in Table 2.
[0088]
[Table 2]

[0089]
　As shown in Table 2, the metal content is detected, at most values obtained by measuring 5 points in φ300mm silicon wafer, either 5 × 10 10 the atom / cm 2 was as follows.
[0090]

　As Experimental Example 3, an experiment was conducted on the relationship between the thickness of the second solvent type and film (filling of the recess) (Table 3). Experimental Example 1 are the experiment to confirm the effect of the second solvent to the polyamine, in Experimental Example 1, the organic substance having two or more carboxyl groups was used.
　In particular, a flat silicon wafer surface, polyethyleneimine (PEI) coating liquid as a first coating liquid (weight average molecular weight of PEI: 25000, the first solvent: water, PEI content: 3 wt%) of a spin coater in coating, followed by a soft bake (100 ° C., 1min) to obtain a coating film (after a soft bake). The thickness of the obtained coating film (after the soft-bake) was measured. The resulting coating thickness (after soft bake) is the last row in Table 3, shown in "After soft bake" column.
　After a soft bake, the surface of the coating film, a 40 mL (each solvent species listed in Table 3) second solvent is applied and then subjected to hard baking 2 minutes at 350 ° C..
　The thickness of the coating film after hard baking was measured.
　In Table 3, in each solvent species, boiling point (bp), log (Pow) , and with shows a SP value, indicating the thickness of the measurement results of the coating film after the hard baking.
[0091]
[table 3]

[0092]
Description ~ of ~ Table 3
, water, NMP, and γ- butyrolactone, the second solvent is a comparative solvent not applicable.
· Log (Pow) "+" in the column indicates the + greater than 1.0.
- last line other than the line "thickness of the film" indicates application of the first coating liquid, a soft bake, the coating of the second solvent, and the thickness of the film after a hard bake.
- last line "membrane thickness" in ( "after the soft-bake") indicates the thickness of the film after undergoing application of the first coating liquid, and a soft bake.
- "N.D." means that there is no measurement results (No Data).
· "NMP" means N- methyl-2-pyrrolidone.
[0093]
　As shown in Table 3, SP value 30 (MPa) 1/2 With the second solvent is less than the thickness of the film after hard baking was thicker.
　In contrast, a comparative solvent, SP value 47.1 (MPa) 1/2 With the water is, the thickness of the film after the hard baking is lowered. The reason is probably because the polyamine is dissolved in comparative solvent (water).
　Furthermore, SP value 30 (MPa) 1/2 Among the second solvent is less than, SP value 24 (MPa) 1/2 With the second solvent is less, the film thickness is particularly thick coating film obtained it was confirmed to be.
[0094]
　From the results of the above Experimental Example 3, SP value 30 (MPa) 1/2 second solvent or less, particularly preferably SP value of 24 (MPa) 1/2 With the second solvent is less, the dissolution of the polyamine in the two coating steps is suppressed, it can be seen that the flattening film buried excellent filling properties into the recess is obtained.
[0095]

　As Example 4, the filling of the carboxyl group second to prepare a coating solution containing a organic comprising two or more and the second solvent, the second solvent type and coating thickness (recess ) experiments on the relationship between were carried out (table 4 below).
[0096]
Preparation of -A film (for comparison) -
　a flat silicon wafer surface, the weight average molecular weight of the polyethylene imine (PEI) coating liquid as a first coating liquid (PEI: 25000, the first solvent: water, PEI content: 3 mass%) was applied by a spin coater, followed by a soft bake (100 ° C., 1min) to give the a film for comparison.
[0097]
Preparation of -B film (for comparison) -
　on the surface of the film A, for comparison dissolved in trimesic acid carboxyl group as the organic material having two or more (TMSA) (3-valent carboxylic acids) Comparison solvent (water) the coating liquid (TMSA content: 3 mass%) was applied to obtain a B film for comparison.
[0098]
Preparation of -C membrane -
　above the surface of the A layer, a second dissolved in a second solvent trimesic acid as the organic substance having a carboxyl group two or more (TMSA) (3-valent carboxylic acid) (ethanol (EtOH)) the coating liquid (TMSA content: 3 mass%) was applied to obtain a C film.
[0099]
Preparation of -D film -
　on the surface of the A layer, the dissolved trimesic acid carboxyl group as the organic material having two or more (TMSA) (3-valent carboxylic acid) in the second solvent (isopropyl alcohol (IPA)) 2 coating solution (TMSA content: 3 mass%) was applied to obtain a D film.
[0100]
- hard bake -
　for each A layer ~ D film was subjected to hard baking for 10 minutes at 400 ° C., the same temperature (400 ° C.) for 20 minutes (30 minutes in total from the hard bake start).
[0101]
- film thickness measurement -
　for A film thickness after soft bake, a hard bake 10 minutes after the film thickness, and the thickness of the hard bake 30 minutes after were measured.
　For B film, film thickness after comparative coating liquid application, the hard bake 10 minutes after the film thickness, and the thickness of the hard bake 30 minutes after measured.
　For each C layer and D layer, film thickness after the second coating liquid coated hard bake 10 minutes after the film thickness, and the thickness of the hard bake 30 minutes after measured.
[0102]
　Based on the measured hard baked 10 minutes after the film thickness and a hard bake 30 minutes after the film thickness by the equation (1) described above, was determined after 30 minutes heat treatment residual film ratio (%). Here, the thickness of the hard bake 10 minutes after the coating as a "film thickness of the heat-treated film 10 minutes" in the formula (1), the thickness of the coating film of a hard bake 30 minutes after the formula (1) " and the thickness of the heat-treated film for 30 minutes. "
　The thickness and 30 minutes heat treatment after film remaining ratio of the film are shown in Table 4 below.
[0103]
[Table 4]

[0104]
Description ~ of ~ Table 4
　thickness after soft baking A film (for comparison), for convenience, as described in "after the second coating liquid coated" column.
　The film thickness after the comparative coating solution coated in the film B (for comparison), for convenience, as described in "after the second coating liquid coated" column.
[0105]
　As shown in Table 4, was coated and soft-baked in the first coating liquid, A film obtained without application of the second coating solution (for comparison), the film is lost due to a hard bake hard bake the relative thickness after 10 minutes became slightly 0.1 nm.
　Moreover, was coated and soft-baked in the first coating solution, further, the B film obtained by applying a comparative coating liquid containing water as comparative solvent (for comparison), the membrane by water in comparison coating solution There was dissolved, a later stage comparative coating liquid coated (i.e., hard baked before step), the was already a slight 6.7nm film thickness.
　For these film A and film B, was coated and soft-baked in the first coating solution, further, the C film obtained by applying a second coating solution containing a EtOH as the second solvent, the second coating solution film did not dissolve even by coating. Rather, the application of the second coating solution, the film thickness before application of the second coating liquid (i.e., after a soft bake A film (for convenience, in "after the second coating liquid coated" column of A film. Hereinafter the same. ) thickness rises above (film see thickness after the second coating liquid coated the C film). As a result, the C film, the film thickness after hard bake 10 minutes is 59 nm, the coating even after hard baking film was not fully remain. Furthermore, 30 minutes after heat treatment the residual film ratio was is 93%, C film had sufficient heat resistance.
　Likewise, the coating and a soft bake of the first coating liquid conducted, further, the D film obtained by applying a second coating solution containing a IPA as the second solvent, film did not dissolve even by application of the second coating solution. rather, the application of the second coating solution thickness prior to application of the second coating solution (i.e., thickness after soft baking a film) film thickness than rises (D The second layer reference thickness after the coating solution application). As a result, the D layer, a film thickness after hard bake is 82 nm, the coating film even after hard baking was sufficiently remained. Further, 30 minutes heat treatment after the film remaining rate is 87%, D film had sufficient heat resistance.
[0106]
　The results of the above Experimental Example 4, SP value 30 (MPa) 1/2 With the second solvent (e.g. EtOH, IPA) or less, solubility of the polyamine to the second coating solution is suppressed, the recess excellent buried planarization film filling properties to be seen can be obtained.
[0107]

　As Experimental Example 5 were carried out with the valence of the carboxylic acids of the carboxyl group as an organic substance having two or more, and heat resistance of the film, the experiments on the relationship (Table 5).
　In particular, a flat silicon wafer surface, polyethyleneimine (PEI) coating liquid as a first coating liquid (weight average molecular weight of PEI: 25000, the first solvent: water, PEI content: 3 wt%) of a spin coater in coating, and then to obtain a soft bake (100 ° C., 1min) to the coating film (after the soft-bake).
　On the obtained coating film (after the soft-bake), second coating solution obtained by dissolving the carboxylic acid shown in Table 5 to the second solvent (EtOH) (acid content: 1.5 wt%) was applied , the thickness of the resulting coating film (hard baked before film thickness) was measured. Next, by hard baking 10 minutes at 380 ° C., the thickness of the resulting coating (thickness after hard bake) was measured.
　Based on the film thickness after the measured hard-baked before the film thickness and the hard-baked at above, the following equation was calculated residual film rate after hard baking (percent). The results are shown in Table 5.
　Residual film ratio after hard baking (%) = (film thickness / hard baked thickness of the film before after hard bake) × 100
[0108]
[table 5]

[0109]
Description ~ of ~ Table 5
types of carboxylic acids are as follows.
　AA ... acetate
　PA ... phthalate
　TMA ... trimellitic acid
　TMSA ... trimesic acid
　PMDA ... pyromellitic acid
and the type of carboxylic acid "no", indicating that did not contain a carboxylic acid in the second coating solution.
[0110]
　As shown in Table 5, the carboxyl group of the second coating solution as an organic compound having two or more trivalent or higher carboxylic acid when used (TMA, TMSA, and PMDA) and the remaining after hard bake film rate is particularly high, in the case of performing the hard bake for 10 minutes at 380 ° C. also, sufficient coating film remained. That is, in this case, it was found that the heat resistance can be formed a particularly high embedding planarization film.
[0111]

　As an experimental example 6, an experiment was conducted on the formation of reaction an amide bond and imide bond by the polyamine and the carboxylic acid.
　Confirmation of formation of an amide bond and imide bond was performed by Fourier transform infrared spectroscopy (FT-IR) measurement.
[0112]
Preparation of -E film (for comparison) -
　a flat silicon wafer surface, polyethyleneimine (PEI) solution (weight average molecular weight of PEI: 25000, solvent: weight ratio [ethanol / water] = 1/3 mixed solvent of, PEI content: 3 mass%) was applied by a spin coater, followed by a soft bake (100 ° C., 1min) to, as a membrane for comparison, to obtain a E film.
　The obtained E film, the FT-IR measurement confirmed the presence of amide bond and imide bond.
　As a result, a peak derived from an amide bond is also a peak derived from the imide bond was also observed.
[0113]
Preparation of -F film (for comparison) -
　a flat silicon wafer surface, polyethyleneimine (PEI) and an aqueous solution of acetic acid (weight average molecular weight of PEI: 25000, solvent: water, PEI content: 1.2 wt%, acetic acid content: 1.4 wt%) was applied by a spin coater, followed by a soft bake (100 ° C., 1min) to, as a membrane for comparison, to obtain a F film.
　The resulting F film, the FT-IR measurement confirmed the presence of amide bond and imide bond.
　As a result, weak peaks derived from amide bond was observed. Peak derived from a imide bond was not observed.
[0114]
Preparation of -G film -
　on the surface of the E layer, the second coating solution is dissolved in trimesic acid carboxyl group as the organic material having two or more (TMSA) (3-valent carboxylic acid) of the second solvent (isopropyl alcohol) (TMSA content: 2 mass%) was applied, then, subjected to a hard bake for 10 minutes at 400 ° C., to obtain a G film.
　The obtained G film, the FT-IR measurement confirmed the presence of amide bond and imide bond.
　As a result, strong peak derived from an amide bond was observed. Peak derived from a imide bond was not observed.
[0115]
Preparation of -H film -
　on the surface of the E layer, the second coating solution obtained by dissolving trimellitic acid carboxyl group as the organic material having two or more (TMA) (3-valent carboxylic acid) of the second solvent (ethanol) (TMA content: 2 mass%) was applied, then, subjected to a hard bake for 2 minutes at 350 ° C., to obtain a H film.
　The obtained H film, the FT-IR measurement confirmed the presence of amide bond and imide bond.
　As a result, a strong peak derived from an amide bond, and a strong peak derived from the imide bond were observed.
[0116]

　embedding planarization film (in particular, the content of the metal element is 5 × 10 per metal element one 10 the atom / cm 2 or less, and the thickness of the planarization layer embedding 100nm embedding planarization film) embodiments satisfying at least one of that least at a the film (i.e., to be removed in a subsequent step, or may be a sacrificial film).
　In particular, in the field of semiconductor device, after some semiconductor processes, there is a demand for removing the flattening film embedded.
[0117]
　The treatment for removing the flattening film embedded include UV-ozone treatment or plasma treatment.
[0118]
　UV ozone treatment to remove the planarizing layer embedding it can be performed by irradiating UV (ultraviolet) in an oxygen atmosphere. By irradiating UV (ultraviolet) in an oxygen atmosphere, ozone is generated, a planarizing film embedded by the ozone is removed.
[0119]
　The plasma treatment for removing a flattening film embedding can be performed using a plasma generated from at least one gas selected from the group consisting of oxygen gas and fluorocarbon gas. The fluorocarbon gas, CF 4 , C 4 F 8 , and the like.
　As the plasma treatment is preferably dry etching in particular, among the dry etching, reactive ion etching is more preferable.
　The plasma treatment for removing the flattening film embedded, for example, can refer appropriate method of dry etching as described in JP 2011-171572.
[0120]
　In the case of using the dicarboxylic acid carboxyl groups of the second coating solution for the organic material having two or more, as a process for removing the flattening film embedded, in addition to the UV ozone treatment and plasma treatment, also it includes a process of heating the embedded planarization film above 380 ° C..
　When organic material having a carboxyl group of the second coating solution two or more is a dicarboxylic acid, particularly excellent in removability of a planarizing film embedded.
[0121]

　As Experimental example 7, experiments were conducted on the removal of the planarization film embedded by UV ozone treatment.
[0122]
Preparation of -I film -
　on a flat silicon wafer surface, polyethyleneimine (PEI) coating solution (weight average molecular weight of PEI: 25000, solvent: weight ratio [ethanol / water] = 1/3, PEI content: 3 wt% ) was applied by a spin coater, followed by a soft bake (100 ° C., 1min) to give a coating film.
　On the surface of the resulting coating film, the second coating solution obtained by dissolving trimellitic acid (TMA) to (trivalent carboxylic acid) in the second solvent (ethanol) (TMA content: 2 mass%) was applied, and then , subjected to hard baking for 10 minutes at 380 ° C., to obtain a I film with a thickness of 100 nm.
[0123]
-UV ozone treatment -
　The obtained I film, under the following conditions, and subjected to UV irradiation under an oxygen atmosphere (UV ozone treatment).
--UV ozone treatment conditions -
　pressure 30 kPa, O 2 / N 2 = 20 (cm 3 /Min.)/600(Cm 3 /Min.),400℃,30Min,UV(ramuda=172nm,14mW/cm 2 )
[0124]
　As a result, the UV ozone treatment under the above conditions, I film with a thickness of 100nm was confirmed to be completely removed in 30 minutes.
[0125]
Preparation of -J film and UV-ozone treatment -
　In the preparation of the I film described above, a second coating solution obtained by dissolving trimellitic acid (TMA) to (trivalent carboxylic acid) in the second solvent (ethanol) (TMA content: 2 mass%), 1,2,3-propane tricarboxylic acid (1, 2, 3-PTCA) (3-valent carboxylic acid) a second coating solution obtained by dissolving the second solvent (isopropyl alcohol) (2 , 3-PTCA content: was changed to 2 mass%) in the same manner as in the preparation of the I layer, to obtain a J film having a thickness of 40 nm.
[0126]
　The obtained J film was subjected to a UV ozone treatment under the above conditions, J film having a thickness of 40nm is, that all removed was confirmed by 10 minutes.
[0127]

　As an experimental example 8, the planarization layer embedded with phthalic acid (dicarboxylic acid) a carboxyl group as an organic substance having two or more, an experiment was performed to remove by heat treatment.
[0128]
Preparation of -K film -
　on a flat silicon wafer surface, polyethyleneimine (PEI) and solution of phthalic acid (PA) is dissolved in a solvent (weight average molecular weight of PEI: 25000, solvent: weight ratio [ethanol / water] = 1/3, PEI content: 1.5 wt%, PA content: 2 mass%) was applied by a spin coater, followed by a soft bake (100 ° C., 1min) to the K film having a thickness of 66.1nm Obtained.
[0129]
Preparation of -L film -
　on a flat silicon wafer surface, the weight average molecular weight of polyethyleneimine (PEI) solution (PEI: 25000, solvent: weight ratio [ethanol / water] = 1/3, PEI content: 1.5 mass %) was applied by a spin coater, followed by a soft bake (100 ° C., 1min) to give a coating film.
　On the surface of the resulting coating film, the second coating solution obtained by dissolving phthalic acid (PA) in the second solvent (ethanol) (PA content: 2 mass%) was applied, with a thickness of 113.9Nm L film It was obtained.
[0130]
- heat removal process -
　for each of said K film and L film was subjected to heat removal treatment for 30 minutes at 380 ° C..
　From the film thickness after the film thickness and heat removal treatment after the soft-bake, the following equation was determined residual film ratio after heat removal process.
　Residual film ratio after heat treatment (%) = (heat treatment after the film layer thickness of the post-film thickness / soft bake) × 100
　As a result, the residual film ratio after heat removal treatment K film is only 0. a 5%, K film was substantially removed by heating removal process.
　Residual film ratio after heat removal processing L film is only 0.5%, L film was substantially removed by heating removal process.
[0131]
　From the results of the above Experimental Example 8, in the case of using the dicarboxylic acid carboxyl groups of the second coating solution for the organic material having two or more, by heating the embedded planarization film above 380 ° C., embedded it was confirmed that the removal of the planarization film.
[0132]

　As an experimental example 9, experiments were conducted for the formation of an amide bond by reaction of a polyamine with a carboxylic acid in the depth direction.
　Confirmation of the formation of the depth direction of the amide bond, time-of-flight secondary ion mass spectrometry: - was carried out by (TOF-SIMS Time of Flight Secondary Ion Mass Spectrometry). TOF-SIMS measurements were carried out in the "TOF.SIMS 5" (ION-TOF Inc.).
[0133]
Preparation of -M film -
　on a flat silicon wafer surface, an aqueous solution of polyethyleneimine (PEI) (weight average molecular weight of PEI: 25000, solvent: water, PEI content: 3 mass%) was applied by a spin coater, followed by soft baking (100 ° C., 1min) to obtain a coating film.
　On the surface of the resulting coating film, the second coating solution obtained by dissolving the trimesic acid carboxyl group as the organic material having two or more (TMSA) (3-valent carboxylic acid) of the second solvent (isopropyl alcohol) (TMSA content : 2 wt%) was applied, then, subjected to a hard bake for 10 minutes at 400 ° C., to obtain a M layer.
　The resulting M film by TOF-SIMS measurement, to confirm the presence or absence of an amide bond in the depth direction.
[0134]
　The results of TOF-SIMS measurement is shown in FIG.
　In Figure 2, the horizontal axis represents the depth of the measurement object (Depth) (Unit: nm) represents, and the vertical axis represents the normalized intensity of the secondary ions (Normalized Intensity).
　In Figure 2, a point depth 0nm shows the surface of the M layer, a region of depth 0nm ~ 100nm indicates M membrane (M-film), deeper than 100nm include silicon wafer (Si-sub. ) shows the.
　In Figure 2,
"C_2H-" is the intensity of the secondary ions derived from organic matter in general,
"CN-" and "13CN-" is the intensity of the secondary ions derived from organic matter in general including nitrogen,
"CNO-" is the intensity of the secondary ions derived from amides,
"C_7H_4NO-" is the intensity of the secondary ion derived from aromatic amides,
"O-" is derived from the oxygen is the intensity of the secondary ions,
"Si-" and "SiO_3-" is the intensity of the secondary ion derived from the silicon and silicon oxide.
[0135]
　As shown in FIG. 2, from the M film surface to the vicinity of the silicon wafer, over substantially the entire depth of the M layer, an amide bond has been detected at substantially the same intensity.
　From the results of TOF-SIMS, organic matter having a carboxyl group of the second coating solution is more than one, not only the coating surface of the first coating solution, it was found to react with the whole coating film.
[0136]
Manufacturing method for an electronic device]
　The method of manufacturing an electronic device of the present embodiment is to provide a method of producing a buried planarizing film of the present embodiment described above, with respect to the semiconductor substrate or the circuit board is a member having the recess, the buried having a planarizing film forming step burying a planarization film.
　The method for manufacturing an electronic device of the present embodiment, as the electronic device, the semiconductor device or the circuit board is manufactured. The electronic device is excellent in filling property for the recess (filling property), with excellent embedding planarization film in heat resistance.
　Embedding planarization film is further excellent in plasma resistance.
[0137]
　The method of manufacturing an electronic device of the present embodiment may have other steps.
　Other processes include processes known in the semiconductor process or the circuit board process.
　For example, a method for fabricating an electronic device of the present embodiment, as other steps, which may have a plasma process.
　As the plasma in the plasma process, helium gas, argon gas, nitrogen gas, ammonia gas, and plasma generated from at least one gas selected from the group consisting of fluorocarbon-based gas and the like.
　The method of manufacturing an electronic device of the present embodiment, even when having a plasma process, damage of the planarization film embedded by the plasma is reduced.
[0138]
　The method of manufacturing an electronic device of the present embodiment, as other steps, may have a removal step of removing a flattening film embedded. This embodiment is particularly suitable when the planarizing film embedded is sacrificial film.
　As a method for removing the planarizing film buried in the removing step, UV ozone treatment described above, or, like plasma treatment as removal treatment of the planarizing film embedding.
　In the case of using a dicarboxylic acid as the organic substance having a carboxyl group two or more, the removal method is a method of heating a semiconductor device or a circuit board planarization film is buried above 380 ° C. it may be.
Example
[0139]
　Following illustratively describes the invention based on examples, the present invention is not limited to the following examples.
[0140]
Example 1

　as a member having a recess, were prepared grooves (aspect ratio 3.6, width 50 nm, depth 180 nm) silicon wafer 1 that has been formed.
[0141]

　polyethyleneimine polyamines (PEI, BASF Corp., brand: Rupasol WF, a weight average molecular weight: 25,000) and, a coating solution is dissolved in water as the first solvent a1 (first coating solution) (PEI content: 3 mass%, pH (25 ℃) 10.5 ) were prepared.
[0142]

　trimesic acid (TMSA) (3-valent carboxylic acid) (Aldrich Co.), isopropyl alcohol as a second solvent; dissolved (IPA Wako Junyaku Co. SC grade) It is allowed coating solution a2 (second coating solution) (TMSA content: 1.5 wt%) was prepared.
[0143]

　the silicon wafer 1 is placed on a spin coater (ABLE Co., Ltd. Ltd.), the groove forming surface of the silicon wafer 1, the coating liquid a1 (first coating liquid) using a pipette Te, after 1mL ejection for 1 second at a rotation speed of 1000 rpm, to obtain a dried coating film is rotated further 60 seconds at a rotation speed of 600 rpm. Then, soft-baked (100 ° C., 1min) in air on a hot plate to give a coating film (after the soft-bake). The silicon wafer coated film (after the soft-bake) is formed, hereinafter also referred to as "film-forming a silicon wafer."
[0144]

　The above film-forming silicon wafer obtained in the first coating step is placed on a spin coater, on the surface of the coating film forming a silicon wafer of a coating film, a coating solution a2 (second coating solution) discharge 1 mL, 1 sec at a rotation speed of 1000 rpm, and dried by further rotated for 60 seconds at a rotation speed of 600 rpm, to obtain a coating film (after second coating liquid coated). The obtained coating film (after the second coating liquid coated), using a hot plate (Apex Co. SPX-1120), under nitrogen, was subjected to hard baking pressure 30 kPa, 400 ° C. for 30 minutes.
　Thus, to obtain a buried planarizing film (buried flattening film 100 in FIG. 1).
[0145]
　The silicon wafer of the cross-section with flattened film embedded produced above was observed by a scanning electron microscope (SEM), it was taken SEM photograph (magnification 200,000 ×).
　The obtained SEM photograph is shown in FIG.
　In Figure 1, "Si" indicates a silicon wafer, "100" denotes a planarizing film embedded.
　As shown in FIG. 1, in the trench, burying the planarization film 100 is found to be filled without creating a void.
[0146]
　The obtained embedding planarization film 100, the film obtained by a hard bake for 30 minutes at 400 ° C. (i.e., the hard-baked remaining film after) it is, and, a carboxyl of the amino group and TMSA of PEI it is considered that the amide bond by the groups which have been generated, considered an excellent film in heat resistance. For the same reason, embedding planarization film 100 is considered an excellent film in plasma resistance.
[0147]
Example 2

　as a member having a recess, it was prepared grooves (aspect ratio 0.67, width 180 nm, depth 120 nm) silicon wafer 2 which has been formed.
　Silicon wafer 2, SiO 2 is a film-coated silicon wafer.
　In particular, SiO by plasma CVD on a silicon wafer 2 and the film is formed, followed by photolithography and dry etching, SiO 2 by removing a portion of the film, the formation of the grooves. This gave the silicon wafer 2.
[0148]

　pyromellitic acid (PMDA) (4 dicarboxylic acid) (produced by Lonza), ethanol as a second solvent; dissolved (EtOH Wako Junyaku Co. SC grade) It is allowed coating solution b2 (second coating solution) (PMDA content: 2.5 wt%) was prepared.
[0149]

　except for the use of the silicon wafer 2 in place of the silicon wafer 1 in the same manner as in the first coating step of Example 1, to obtain a coating film forming a silicon wafer.
[0150]

　on the surface of the film-forming silicon wafer obtained in the first coating step, in the same manner as in the second coating step of Example 1 using the second coating liquid b2 coating (second coating was obtained after the liquid coating). The obtained coating film (after the second coating liquid coated), except for changing the temperature to 380 ° C. was subjected to hard baking in the same manner as in Example 1.
　The silicon wafer of the cross-section with flattened film buried prepared above, and observed with a transmission electron microscope (TEM), were taken TEM photo (magnification of 100,000 times).
　The resulting TEM photograph shown in FIG.
　In Figure 3, "Si" indicates a silicon wafer, "SiO 2 " is SiO 2 shows the film, "100" denotes a planarizing film embedded.
　As shown in FIG. 3, in the trench, burying the planarization film 100 is found to be filled without creating a void.
[0151]
Example 3

　as a member having a recess, it was prepared grooves (aspect ratio 2, the width 100 nm, depth 200 nm) silicon wafer 3 is formed.
[0152]

　phthalic anhydride (PA) (2-valent carboxylic acid) (Aldrich Co.), isopropyl alcohol as a second solvent; the (IPA Wako Junyaku Co. SC grade) was dissolved coating solution c2 (second coating solution) (PA content: 3.0 wt%) was prepared.
[0153]

　except for the use of the silicon wafer 3 in place of the silicon wafer 1 in the same manner as in the first coating step of Example 1, to obtain a coating film forming a silicon wafer.
[0154]

　on the surface of the film-forming silicon wafer obtained in the first coating step, in the same manner as in the second coating step of Example 1 using the second coating liquid c2 coating (second coating was obtained after the liquid coating).
　The obtained coating film (after the second coating liquid coated), using a hot plate (Apex Co. SPX-1120), under nitrogen, was subjected to hard baking pressure 30 kPa, 350 ° C. for 40 minutes.
　The silicon wafer of the cross-section with flattened film embedded produced above was observed by a scanning electron microscope (SEM), it was taken SEM photograph (magnification 150,000 ×).
[0155]
　The obtained SEM photograph is shown in FIG.
　In Figure 4, "Si" indicates a silicon wafer, "100" denotes a planarizing film embedded.
　As shown in FIG. 4, in the trench, burying the planarization film 100 is found to be filled without creating a void.
[0156]
Example 4

　pyromellitic anhydride (PMDA) (4 dicarboxylic acid) (produced by Lonza), ethanol as a second solvent (EtOH; Wako Pure Chemical the coating liquid was dissolved in manufacturing SC grades) d2 (second coating solution) (PMDA content: 2.0 wt%) was prepared.
[0157]

　except for the use of the silicon wafer 3 in place of the silicon wafer 1 in the same manner as in the first coating step of Example 1, to obtain a coating film forming a silicon wafer.
[0158]

　on the surface of the film-forming silicon wafer obtained in the first coating step, in the same manner as in the second coating step of Example 1 using the second coating liquid d2 coating (second coating was obtained after the liquid coating).
　The obtained coating film (after the second coating liquid coated), using a hot plate (Apex Co. SPX-1120), under nitrogen, was subjected to hard baking pressure 30 kPa, 400 ° C. for 10 minutes.
　The silicon wafer of the cross-section with flattened film embedded produced above was observed by a scanning electron microscope (SEM), it was taken SEM photograph (magnification 150,000 ×).
　The obtained SEM photograph is shown in FIG.
　In Figure 5, "Si" indicates a silicon wafer, "100" denotes a planarizing film embedded.
　As shown in FIG. 5, in the trench, burying the planarization film 100 is found to be filled without creating a void. Incidentally, the particulate matter in the planarization film 100 buried in FIG. 5, an uneven made to the cross section of the flattening film 100 buried at SEM observation sample prepared.
[0159]
Comparative Example 1
　except for using the silicon wafer 3 in place of the silicon wafer 1 in the same manner as in the first coating step of Example 1, to obtain a coating film forming a silicon wafer.
　Without the application of the second coating solution to said film-forming silicon wafer coating, to the film-forming silicon wafer using a hot plate (Apex Co. SPX-1120), under nitrogen, the pressure 30 kPa, and subjected to hard baking 30 minutes at 350 ° C.. Thus, to obtain a comparative film with a silicon wafer.
　The silicon wafer of the cross-section with a comparative film produced above was observed by a scanning electron microscope (SEM), it was taken SEM photograph (magnification 150,000 ×).
　The obtained SEM photograph is shown in FIG.
　In Figure 6, "Si" indicates a silicon wafer, "101" indicates the comparative film, "102" indicates the top of the gap groove.
　As shown in FIG. 6, not inside of the trench is filled with comparison film 101, it was found that the gap 102 occurs in the top of the groove.
　Film thickness was heat-treated for 30 minutes with respect to the film thickness of the film subjected to heat treatment for 10 minutes at 350 ° C. was 16%.
　This result, polyamines of the first coating liquid is considered to indicate that it has contracted by hard baking 350 ° C..
　From the above results, the film made of only the polyamine which has not reacted with organic matter having two or more carboxyl groups (e.g., the comparative film) was found to heat resistance is insufficient.
[0160]
　Japanese disclosure of patent application 2015-069833 its entirety is incorporated herein by reference.
　All documents described herein, patent applications, and technical standards, each individual publication, patent applications, and to the same extent as if it is marked specifically and individually incorporated by techniques standard reference, It incorporated by reference herein.

The scope of the claims
[Claim 1]
　A region including the concave portion of the member having a recess, a first coating step of filling the first coating liquid in the recess by applying a first coating solution containing a polyamine and a first solvent,
　said first coating of said member in a region including the recess liquid is embedded, SP value is the organic matter and a boiling point of 200 ° C. or less having at least two carboxyl groups is 30 (MPa) 1/2 second coating solution containing a second solvent is less by applying, a second coating step of forming a planarizing film embedded to planarize the region including the concave portion of the member
having a method for producing a planarizing film embedded.
[Claim 2]
　Organic material having a carboxyl group two or more, a divalent or higher carboxylic acids, method for producing a buried planarizing film of claim 1.
[Claim 3]
　The content of the polyamine first coating solution is not more than 1.0 mass% to 20 mass%, the production method of embedding planarization film according to claim 1 or claim 2.
[Claim 4]
　Wherein the first solvent has a boiling point is not less 200 ° C. or less, a hydrophilic, method for producing a planarizing film embedded according to any one of claims 1 to 3.
[Claim 5]
　The buried with a planarization film amide bond, the manufacturing method of embedding planarization film according to any one of claims 1 to 4.
[Claim 6]
　The recess has a width is at 250nm or less, the ratio of the depth [depth / width] is 0.3 or more and, embedding planarization film according to any one of claims 1 to 5 to the width the method of production.
[Claim 7]
　Content per unit area of the metal element in the embedding planarization film is a metal element per type, 5 × 10 10 the atom / cm 2 or less, according to any one of claims 1 to 6 the method of manufacturing the embedded planarization film.
[8.]
　The manufacturing method of embedding planarization film according to any one of claims 1 to 7, with respect to the semiconductor substrate or the circuit board is a member having the recess, planarized buried to form the buried planarization film having a film forming process, a method for fabricating an electronic device.
[Claim 9]
　Furthermore, having a removal step of removing the buried planarization film, method of manufacturing an electronic device according to claim 8.