阅读说明：本技术 基板图案填充组合物及其使用 (Substrate pattern filling composition and use thereof ) 是由 堀场优子 久保木博子 长原达郎 于 2020-04-15 设计创作，主要内容包括：本发明提供一种能够抑制图案倒塌的基板图案填充组合物及使用其的方法。一种基板图案填充组合物,包括(A)第一溶质、(B)第二溶质和(C)溶剂。还提供了使用其的方法。(The invention provides a substrate pattern filling composition capable of inhibiting pattern collapse and a method using the same. A substrate pattern filling composition includes (A) a first solute, (B) a second solute, and (C) a solvent. Methods of using the same are also provided.)

1. A substrate pattern filling composition comprising (a) a first solute, (B) a second solute, and (C) a solvent; wherein

(A) The first solute having at least one of an amino group, a hydroxyl group, and a carbonyl group, with the proviso that the first solute has at most one hydroxyl group per molecule;

(B) the second solute having at least one of an amino group, a hydroxyl group, and a carbonyl group, with the proviso that the second solute has at most one hydroxyl group per molecule;

(A) the first solute and (B) the second solute are different substances; and is

Preferably, (a) the first solute and/or (B) the second solute each independently comprise a 5-or 6-membered hydrocarbon ring or heterocyclic ring.

2. The composition according to claim 1, wherein a film is formed from the substrate pattern-filling composition filled in the substrate pattern, the film being removed from the substrate pattern by independently vaporizing (a) the first solute and/or (B) the second solute, respectively;

preferably the gasification is sublimation;

preferably, when the film formed of the substrate pattern filling composition is removed, heating (more preferably 70 ℃ or higher) and/or pressure reduction (more preferably 80kPa or lower) is not performed.

3. The composition of claim 1 or 2, wherein in (a) the first solute and/or (B) the second solute, the amino group and/or the carbonyl group, respectively, is independently part of a hydrocarbon ring or a heterocyclic ring to which the hydroxyl group is directly attached;

preferably, (a) the first solute and/or (B) the second solute each independently have a main skeleton of cage-type steric configuration;

preferably, each of (a) the first solute and/or (B) the second solute independently has 1 to 5 amino groups, 1 to 3 carbonyl groups, and/or 1 hydroxyl group per molecule.

4. The composition according to at least one of claims 1 to 3, wherein the molecular weight of (A) the first solute and/or (B) the second solute is independently from 80 to 300, respectively.

5. The composition according to at least one of claims 1 to 4, wherein the sum of the mass of (A) the first solute and (B) the second solute is 1 to 40 mass% based on the mass of the substrate pattern filling composition;

preferably, the mass ratio of (a) the first solute to (B) the second solute is from 99:1 to 1: 99;

preferably, the mass of the (C) solvent is 30 to 99 mass% based on the mass of the substrate pattern filling composition.

6. The composition according to at least one of claims 1 to 5, wherein (C) the solvent comprises an organic solvent comprising at least 1 selected from the group consisting of alcohols, alkanes, ethers, lactate esters, aromatics, ketones, amides and lactones.

7. Composition according to at least one of claims 1 to 6, characterized in that (A) the first solute, (B) the second solute and (C) the solvent have a boiling point bp at one atmosphere pressure_A、bp_BAnd bp_CSatisfy bp_A＞bp_B＞bp_C；

Preferably, the saturated vapor pressure vp of (A) the first solute, (B) the second solute and (C) the solvent at 25 ℃ and 1 atmosphere_A、vp_BAnd vp_CSatisfy vp_A＜vp_B＜vp_C。

8. The composition according to at least one of claims 1 to 7, wherein (A) the first solute is represented by formula (A), (B) the second solute is represented by formula (B):

Cy₁₁and Cy₁₂Each independently is a saturated or unsaturated hydrocarbon ring or heterocyclic ring;

Cⁿ¹each is carbon, n1 is an integer of 10 to 19, Cⁿ¹The rest bonding end is bonded with H;

Cⁿ¹can also be respectively and independently replaced by-Cⁿ¹R_n1-、-Cⁿ¹R_n1R_n1’-、-Cⁿ¹(OH)-、-Cⁿ¹(＝O)-、-Nⁿ¹H-, and/or-Nⁿ¹R_n1-；

R_n1And R_n1’Are each independently C_1～5Alkyl, -NH₂And/or C_1～5Aminoalkyl radical, R_n1And/or R_n1’Can be combined with other R_n1、R_n1’And/or Cⁿ¹Bonding to form a ring;

n₁₁、n₁₂and n₁₃Each independently 0 or 1:

Cy₂₁and Cy₂₂Each independently is a saturated or unsaturated hydrocarbon ring or heterocyclic ring;

Cⁿ²each is carbon, n2 is an integer of 20 to 29, Cⁿ²The remaining bonding end of (2) is bonded with H;

Cⁿ²can be respectively and independently replaced by-Cⁿ²R_n2-、-Cⁿ²R_n2R_n2’-、-Cⁿ²(OH)-、-Cⁿ²(＝O)-、-Nⁿ²H-, and/or-Nⁿ²R_n2-；

R_n2And R_n2’Are each independently C_1～5Alkyl, -NH₂And/or C_1～5Aminoalkyl radical, R_n2And/or R_n2’Can be combined with other R_n2、R_n2’And/or Cⁿ²Bonding to form a ring;

n₂₁、n₂₂and n₂₃Each independently is 0 or 1.

9. The composition according to at least one of claims 1 to 8, (A) the first solute and (B) the second solute are each independently any one of phthalic anhydride, caffeine, melamine, 1, 4-benzoquinone, camphor, hexamethylenetetramine, hexahydro-1, 3, 5-trimethyl-1, 3, 5-triazine, 1-adamantanol, 1, 4-diazabicyclo [2.2.2] octane, borneol, (-) -borneol, (±) -isoborneol, 1, 2-cyclohexanedione, 1, 3-cyclohexanedione, 1, 4-cyclohexanedione, 3-methyl-1, 2-cyclopentadione, (±) -camphorquinone, (+) -camphorquinone, or 1-adamantanamine.

10. The composition according to at least one of claims 1 to 9, further comprising (D) a third solute;

preferably, the composition further comprises (E) a fourth solute;

here, it is assumed that the boiling points of (D) the third solute and (E) the fourth solute are bp at 1 atmosphere_D、bp_ESaturated vapor pressure at 25 ℃ and 1 atm is vp_D、vp_E，

Then bp is satisfied_C＜bp_E＜bp_D＜bp_B＜bp_A；

Preferably, vp is satisfied_A＜vp_B＜vp_D＜vp_E＜vp_C。

11. Composition according to at least one of claims 1 to 10, characterized in that the substrate pattern is washed with a cleaning liquid and used to replace the liquid present on the substrate before the substrate pattern filling composition is applied.

12. The composition according to at least one of claims 1 to 11, further comprising (F) other additives;

here, (F) other additives include a surfactant, an antibacterial agent, a bactericide, a preservative, an antifungal agent, an acid and/or a base.

Preferably, the (F) other additive is 0 to 20 mass% as compared to the sum of the mass of the (a) first solute and the (B) second solute.

13. Composition according to at least one of claims 1 to 12, characterized in that the surface of the substrate where the pattern filled by the composition is present is selected from the group consisting of Si, Ge, SiGe, Si₃N₄、TaN、SiO₂、TiO₂、Al₂O₃、SiON、HfO₂、T₂O₅、HfSiO₄、Y₂O₃、GaN、TiN、TaN、Si₃N₄NbN, Cu, Ta, W, Hf, Al;

preferably, the surface of the substrate is a semiconductor.

14. A method for manufacturing a device, comprising filling the composition of at least one of claims 1 to 13 onto a substrate pattern to form a film, and removing the film by vaporizing the film.

Technical Field

The present invention relates to a substrate pattern filling composition and use thereof.

Background

The following procedures are well known: in the manufacture of devices (electronic parts) such as semiconductor devices and liquid crystal display devices, a fine uneven pattern is formed on a wafer surface by film formation, photolithography, etching, or the like, and then the wafer surface is cleaned. Due to the high integration requirement of LSI, the device tends to be fine, and the above-described concave-convex pattern requires a narrower width and a higher aspect ratio. In cleaning a surface of a wafer on which an uneven pattern is formed, a technique of removing contaminants by supplying a cleaning liquid such as ion-exchanged water (DIW) or an organic solvent is known. However, if the uneven pattern is very fine, there is a problem that pattern collapse occurs due to surface tension of the cleaning liquid and capillary phenomenon at the time of drying treatment after removing contaminants.

In this case, there is an attempt to clean the pattern while preventing the pattern from collapsing by sublimating the sublimable substance by replacing the cleaning liquid or the like with a filling treatment agent containing the sublimable substance. Patent document 1 provides a technique of dropping a filling treatment agent heated and melted once to a sublimation substance into an uneven pattern, and cooling the filling treatment agent to deposit the sublimation substance in the uneven pattern instead of the cleaning liquid. Patent document 2 provides a technique of reducing the solubility in a sublimable substance solvent by cooling or the like to solidify the solvent, and removing the solvent by sublimation. Patent document 3 provides a pattern forming method using a gap filling compound.

Documents of the prior art

Patent document

Patent document 1: japanese patent laid-open publication No. 2013-42094

Patent document 2: international publication of WO2019/021664

Patent document 3: international publication of WO2017/174476

Non-patent document

Non-patent document 1: pages 22 to 25 of Toshiba Review Vol.59No.8(2004)

Disclosure of Invention

Problems to be solved by the invention

The present inventors have recognized that there is a need for improvement in one or more of the problems. Examples of these include the following: the substrate pattern cannot be cleaned; pattern collapse can occur when the substrate pattern is cleaned; cannot be filled into a fine substrate pattern; the inability to form a film on a fine substrate pattern; film formation could not be achieved without heating; heating or reducing pressure is necessary to remove the film; vaporization of the solute in the composition does not remove the film from the substrate pattern; the solvent cannot be vaporized first and then the solute can be gradually vaporized; the amount of solute remaining in the removed substrate pattern is large; the solubility of the solid component in the solvent is low; the process of removing the film from the substrate pattern cleaning process is complicated; damage to other layers or structures near the substrate pattern during cleaning of the substrate pattern; the finished product rate is poor; the stability of the composition is low.

The present invention has been made in view of the above-mentioned technical background, and provides a substrate pattern filling composition containing (a) a first solute, (B) a second solute, and (C) a solvent, and a method for using the same.

Means for solving the problems

The substrate pattern filling composition according to the present invention includes (a) a first solute, (B) a second solute, and (C) a solvent. (A) The first solute has at least one of an amino group, a hydroxyl group, or a carbonyl group. With the proviso that the first solute has at most one hydroxyl group per molecule. (B) The second solute has at least one of an amino group, a hydroxyl group, or a carbonyl group. Provided that the second solute has at most one hydroxyl group per molecule. (A) The first solute and (B) the second solute are different substances.

In the substrate pattern filling composition according to the present invention, it is a preferred form that (a) the first solute, (B) the second solute, and (C) the solvent have boiling points bpA, bpB, and bpC satisfying bpA > bpB > bpC at one atmospheric pressure.

The present specification provides a method of manufacturing a device, the method including filling a substrate pattern with a substrate pattern filling composition according to the present invention to form a film, and removing the film by vaporization.

ADVANTAGEOUS EFFECTS OF INVENTION

By using the substrate pattern filling composition of the present invention, one or more of the following effects can be obtained.

The substrate pattern can be cleaned; pattern collapse in the substrate pattern cleaning process can be suppressed; fine substrate patterns can be filled; a film can be formed on the fine substrate pattern; the film can be formed without heating; removing the film without heating and/or reducing pressure; removing the film from the substrate pattern by vaporization of the solute in the composition; by vaporizing the solvent first and then gradually vaporizing the solute, collapse of the substrate pattern can be suppressed; the amount of solute remaining in the substrate pattern after removal can be reduced; a composition having good solubility of the solid component in the solvent can be obtained; the film removing procedure in the substrate pattern cleaning process can be reduced, and the damage to other layers or structures near the substrate pattern can be reduced; the yield is good; the composition has excellent stability.

Drawings

Fig. 1 is an explanatory view of a pattern forming method according to the present invention.

Detailed Description

The embodiments of the present invention will be described in detail below.

Definition of

The definitions and examples provided in this paragraph are followed unless the specification indicates otherwise.

The singular forms "a", "an" and "the" mean "at least one". Elements of a concept can be represented by a plurality of species, and when quantities (e.g., mass%, mole%) are expressed, the quantities refer to the sum of the plurality of species.

"and/or" includes all combinations of elements or uses thereof.

When numerical ranges are expressed as "" to "" or "" they include both endpoints, the units are general. For example, 5 to 25 mol% means 5 mol% or more and 25 mol% or less.

“C_x-y”、“C_x-C_y"and" C_x"etc. describe refers to the number of carbons in a molecule or substituent. E.g. C_1～6Alkyl refers to an alkyl chain having 1 to 6 carbons (methyl, ethyl, propyl, butyl, pentyl, hexyl, etc.).

If the polymer has multiple types of repeating units, these repeating units are copolymerized. These copolymers may be any of alternating copolymers, random copolymers, block copolymers, graft copolymers, or mixtures thereof. When the polymer, resin are represented by structural formulae, n, m, etc. are also written in parentheses, indicating the number of repetitions.

The temperature units are given in degrees celsius. For example, 20 degrees means 20 degrees celsius.

The additive refers to the compound itself having this function (for example, in the case of a base generator, the compound itself generating a base). In some embodiments, the compound is dissolved or dispersed in a solvent and added to the composition. As an embodiment of the present invention, such a solvent is preferably contained in the composition according to the present invention as (C) a solvent or other component.

Substrate pattern filling composition

The substrate pattern filling composition according to the present invention includes specific (a) a first solute, (B) a second solute, and (C) a solvent. In addition, it may contain other components as necessary.

In the present invention, the substrate pattern refers to a pattern formed by processing a substrate, and does not include a pattern formed by other films or layers on the substrate. For example, a method of forming a resist pattern on a bare wafer is not included in the substrate pattern of the present invention. The substrate pattern filling composition refers to a composition filling (allowing overflow) between patterns of a substrate pattern, and more preferably a manner of forming a film thereafter.

The following description will be made for each component.

(A) A first solute, and (B) a second solute

The (a) first solute according to the present invention has at least one of an amino group, a hydroxyl group or a carbonyl group. With the proviso that the first solute has at most one hydroxyl group per molecule. (B) The second solute has at least one of an amino group, a hydroxyl group, or a carbonyl group. Provided that the second solute has at most one hydroxyl group per molecule. (A) The first solute and (B) the second solute are different substances.

Preferably, (a) the first solute and/or (B) the second solute each independently comprise a five-membered or six-membered ring of a hydrocarbon ring or a heterocyclic ring. In one embodiment of the present invention, when the film formed from the substrate pattern filling composition is subsequently vaporized, (B) the second solute is preferably vaporized before (a) the first solute.

As one embodiment of the present invention, the substrate pattern filling composition according to the present invention is filled into a substrate pattern to form a film. Preferably, (C) the solvent is first vaporized, the solid component is formed into a film, and then the solid component is vaporized to remove the film. More preferably, (a) the first solute and (B) the second solute are independently vaporized as solid components. The preferred mode of vaporization is sublimation. Preferably, sublimation is the direct change of part of the solid component from a solid phase to a gas phase. More preferably, sublimation is the direct change of substantially all solid components from a solid phase to a gas phase. In addition, as another form, (a) the first solute and/or (B) the second solute are substances having sublimation points that change from a solid phase to a gas phase at room temperature without passing through the liquid phase. In another preferred embodiment, (a) the first solute and/or (B) the second solute is a substance that changes from a solid phase to a gas phase through a liquid phase when heated under normal pressure, and may be a substance that has a melting point and that sublimes slowly below the melting point.

Preferably, when the film formed of the substrate pattern filling composition is removed, heating and/or pressure reduction is not performed. The heating is more preferably 70 ℃ or higher, more preferably 80 ℃ or higher, and still more preferably 90 ℃ or higher, and the upper limit is more preferably 200 ℃ or lower, still more preferably 170 ℃ or lower, and still more preferably 150 ℃ or lower. The reduced pressure referred to herein is more preferably 80kPa or less, still more preferably 50kPa or less, yet more preferably 20kPa or less, and the lower limit is more preferably 1kPa or more, still more preferably 5kPa or more, and still more preferably 10kPa or more. Further, an advantage of the present invention is that when the above-described film is removed in the present invention, the cooling process described in patent document 1 is not necessary. As another mode of the present invention, the present invention is also advantageous in that the gas injection is not necessary for removing the film. Examples of the gas mentioned here include atmospheric air, argon gas and nitrogen gas, and examples thereof include a gas using a reduced humidity and oxygen concentration.

In order to clean the substrate pattern, (a) the first solute and/or (B) the second solute are preferably substances that are easily vaporized from the viewpoint of reducing the amount remaining in the substrate pattern. In order to further reduce the residual amount of the solid component having such characteristics, a heating step may be added. In one embodiment of the present invention, the substrate pattern filling composition may be heated for removing a film formed from the substrate pattern filling composition under conditions of 35 to 150 ℃ (more preferably 35 to 120 ℃, still more preferably 40 to 110 ℃, still more preferably 40 to 100 ℃) for 10 to 180 seconds (more preferably 10 to 120 seconds, still more preferably 10 to 90 seconds).

In one embodiment of the present invention, in each of (a) the first solute and/or (B) the second solute, independently, an amino group and/or a carbonyl group is a part of a hydrocarbon ring or a heterocyclic ring, and a hydroxyl group is directly added to the hydrocarbon ring or the heterocyclic ring. That is, the compound having a carboxyl group does not belong to (a) the first solute and (B) the second solute in this embodiment. Preferably, (a) the first solute and/or (B) the second solute each independently have a main skeleton of a cage-type steric structure. The cage type stereo structure may be, for example, 1, 4-diazabicyclo [2.2.2] octane (hereinafter referred to as DABCO). It is advantageous to be able to suppress umbrella height compared to molecular weight. Alternatively, it is also preferable that an amino group is independently added directly to the ring in each of (a) the first solute and/or (B) the second solute. For example, 1-adamantanamine has a main skeleton of cage type steric structure, and an amino group is not a part of a ring but is directly added to the ring.

As a preferred mode of the present invention, (a) the first solute and/or (B) the second solute each independently has 1 to 5 amino groups (more preferably 1 to 4, further preferably 2 to 4), 1 to 3 carbonyl groups (more preferably 1 to 2) and/or 1 hydroxyl group per molecule. The amino group also includes the manner in which the bonded end of the nitrogen atom is used for a double bond, for example, C ═ N- (imino). The number of amino groups is calculated by the number of nitrogen atoms present in a molecule. A form having any one of an amino group, a carbonyl group, or a hydroxyl group in one molecule is a preferred mode of the present invention. In another embodiment, it is also preferable that one molecule has a carbonyl group and an amino group.

In one embodiment of the present invention, the molecular weight of (a) the first solute and/or (B) the second solute is independently 80 to 300 (preferably 90 to 200). Without being bound by theory, if the molecular weight is too large, energy is required for gasification and it is considered that it is not suitable for the process of the present invention.

As a preferable embodiment of the present invention, the sum of the masses of (a) the first solute and (B) the second solute is 1 to 40 mass% (more preferably 1 to 30 mass%, further preferably 2 to 20 mass%) based on the mass of the substrate pattern filling composition. Although not being bound by theory, it is believed that if the amount of solute is too small, film formation becomes difficult and the effect of suppressing collapse of the substrate pattern decreases.

Preferably, the mass ratio of (a) the first solute to (B) the second solute is 99:1 to 1:99 (more preferably 95:5 to 5:95, further preferably 90:10 to 10:90, still further preferably 80:20 to 20: 80). As another preferable mode of the present invention, the mass ratio of (B) the second solute to (a) the first solute may be 0.5 to 20 (more preferably 1 to 20, still more preferably 5 to 20).

In one embodiment of the present invention, (a) the first solute is represented by formula (a).

Wherein, Cy₁₁And Cy₁₂Each independently a saturated or unsaturated hydrocarbon ring or heterocyclic ring. Preferably Cy is used₁₁And Cy₁₂And at the same time, a saturated or unsaturated hydrocarbon ring or heterocyclic ring, more preferably Cy₁₁And Cy₁₂And is a saturated hydrocarbon ring or heterocyclic ring. The heterocyclic ring mentioned herein may be C which forms a ringⁿ¹Substituted to form a heterocycle.

Cⁿ¹Each is carbon, and n1 is an integer of 10 to 19 (i.e., C)¹⁰、C¹¹、……C¹⁹)。Cⁿ¹The remaining bonding end of (a) is bonded to H.

Cⁿ¹Can be respectively and independently replaced by-Cⁿ¹R_n1-、-Cⁿ¹R_n1R_n1’-、-Cⁿ¹(OH)-、-Cⁿ¹(＝O)-、-Nⁿ¹H-, and/or-Nⁿ¹R_n1-. However, at least 1Cⁿ¹Is replaced by at least any one of the above. Of course, non-existent elements are excluded from this supplemental clause. For example, when n₁₁＝n₁₂When 0, at least one of C10 to C14 may be substituted. Preferably not replacing adjacent Cn1 at the same time.

R_n1And R_n1’Are each independently C_1～5Alkyl (preferably C)_1～4More preferably C_1～3)、-NH₂And/or C_1～5Aminoalkyl radical (preferably C)_1～4More preferably C_1～3More preferably C₁)，R_n1And/or R_n1’It is also possible to combine the compounds with other R_n1、R_n1’And/or Cⁿ¹The bond forms a ring. R_n1And R_n1’With other R_n1、R_n1’And/or Cⁿ¹The form of a ring by bonding is preferable.

n₁₁、n₁₂And n₁₃Each independently is 0 or 1. It is preferred that n is₁₁0. It is preferred that n is₁₂1. It is preferred that n is₁₃＝1。

In one embodiment of the present invention, (B) the second solute is represented by formula (B).

Cy₂₁、Cy₂₂、R_n2、R_n2’、n₂₁、n₂₂And n₂₃Are each independently of Cy₁₁、Cy₁₂、R_n1、R_n1’、n₁₁、n₁₂And n₁₃The same is true.

Cⁿ²Are each independently of Cⁿ¹The same is true. n2 is an integer of 20 to 29 (i.e., C)²⁰、C²¹、……C²⁹)。n2(20～29) Examples and descriptions of (1) correspond to n1(10 to 19), respectively and independently.

As one embodiment of the present invention, the following compound may be represented by formula (a). In this case, Cy₁₁Is a saturated six-membered hydrocarbon ring, n₁₁＝0、n₁₂＝1。C¹²Can be used as-C¹²R₁₂R_12’-replacing. R₁₂Is methyl (C)₁Alkyl), R_12′Is isopropanol (C)₃Alkyl groups). R_12′And C¹⁵The bond forms a ring. C¹³quilt-C¹³(═ O) -substitution, C¹⁴quilt-C¹⁴(═ O) -alternative. The following compounds have 2 carbonyl groups per molecule. Overall, the following compounds have a main skeleton of a cage-type three-dimensional structure.

In one embodiment of the present invention, the following compound may be represented by formula (B). In this case, Cy₂₁Is a saturated six-membered hydrocarbon ring, n₂₁＝0，n₂₂＝1。C²⁰Can be-N²⁰R₂₀-substitution, C²²Can be-N²²R₂₂-substitution, C²⁴Can be-N²⁴R₂₄-replacing. R₂₀Is aminomethyl (C)₁)，R₂₂And R₂₄Is methyl (C)₁)。R₂₀、R₂₂And R₂₄The bond forms a ring. The following compounds have 4 amino groups per molecule. Overall, the following compounds have a main skeleton of a cage-type three-dimensional structure.

As one embodiment of the present invention, the following compound may be represented by formula (a). In this case, Cy₁₁Is a saturated six-membered hydrocarbon ring (heterocyclic in the following substitution). n is₁₁＝0、n₁₂＝1。C¹²Can be-C¹²R₁₂R_12’-substitution, C¹⁴Can be-C¹⁴R₁₄-substitution, C¹⁰Can be-C¹⁰R₁₀-replacing. R₁₂is-NH₂，R_12’Is ethyl (C)₂)，R₁₄And R₁₀Is methyl (C)₁)。R_12’、R₁₄And R₁₀The bond forms a ring. The following compounds have 1 amino group per molecule. Overall, the following compounds have a main skeleton of a cage-type three-dimensional structure.

As one embodiment of the present invention, the following compound may be represented by formula (B). In this case, Cy₂₁Is an unsaturated six-membered hydrocarbon ring (phenyl), Cy₂₂A saturated five-membered hydrocarbon ring (heterocyclic in the following substitution). n is₂₁＝n₂₂＝1、n₂₃＝0。C²⁶Can be-C²⁶(═ O) -substitution, C²⁸Can be-C²⁸(═ O) -alternative. The following compounds have 2 carbonyl groups per molecule. Overall, the following compounds can be represented as structural formulae in plan view, without having a main skeleton of a cage type three-dimensional structure.

Although the scope of the present invention is not limited by the scope of the present invention, specific examples of (a) the first solute and/or (B) the second solute may be listed below, respectively. That is, they are independently phthalic anhydride, caffeine, melamine, 1, 4-benzoquinone, camphor, hexamethylenetetramine, hexahydro-1, 3, 5-trimethyl-1, 3, 5-triazine, 1-adamantanol, 1, 4-diazabicyclo [2.2.2] octane, borneol, (-) -borneol, (±) -isoborneol, 1, 2-cyclohexanedione, 1, 3-cyclohexanedione, 1, 4-cyclohexanedione, 3-methyl-1, 2-cyclopentanedione, (±) -camphorquinone, (-) -camphorquinone, (+) -camphorquinone, and 1-adamantanamine.

Specific examples of (a) the first solute and/or (B) the second solute are represented by the following structures.

(A) The first solute is composed of a single type of compound and is not represented in multiple types. For example, embodiments in which both phthalic anhydride and caffeine are included in the composition as (a) the first solute are outside the scope of the present invention. It is noted that embodiments comprising phthalic anhydride as (a) the first solute and caffeine as (B) the second solute in the composition may be included within the scope of the present compositions.

However, the optical isomers listed in the specific examples may be used as a mixture. The same applies to (B) the second solute, and (D) the third solute and (E) the fourth solute described later.

(A) The first solute and/or (B) the second solute do not exclude trace impurities from being mixed with. For example, when the first solute (a) is phthalic anhydride, the impurity (other than phthalic anhydride) is allowed to be present in an amount of 2 mass% or less (preferably 1 mass% or less, more preferably 0.1 mass% or less, and further preferably 0.01 mass% or less) based on the total amount of the first solute (a).

(C) Solvent(s)

The substrate pattern filling composition of the present invention comprises (C) a solvent. (C) The solvent preferably contains an organic solvent. In one embodiment of the present invention, the solvent (C) is volatile. Preferably more readily vaporized than water. As one embodiment of the present invention, a solvent vaporized by spin drying is suitable. For example, the boiling point of the solvent (C) at 1 atm is preferably 50 to 200 ℃, more preferably 60 to 170 ℃, and still more preferably 70 to 150 ℃. (C) The solvent may also contain a small amount of pure water. Pure water (0 mass%) is not contained is a preferred embodiment of the present invention. In the present specification, the pure water is preferably ion-exchanged water.

As a preferred embodiment of the present invention, the components (including additives) contained in the substrate pattern filling composition are dissolved in the (C) solvent. The substrate pattern filling composition in this manner is considered to have good embedding properties and/or film uniformity.

Examples of the organic solvent include alcohols such as methanol (MeOH), ethanol (EtOH) and isopropyl alcohol (IPA), alkanes such as hexane, heptane and octane, and ethers such as ethylbutyl ether, dibutyl ether and Tetrahydrofuran (THF). Esters such as methyl lactate and Ethyl Lactate (EL), aromatic hydrocarbons such as benzene, toluene and xylene, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, 2-heptanone, cyclopentanone and cyclohexanone, amides such as N, N-dimethylacetamide and N-methylpyrrolidone, and lactones such as γ -butyrolactone. Examples of the ethers include ethylene glycol monoalkyl ethers such as ethylene glycol monomethyl ether and ethylene glycol monoethyl ether, ethylene glycol monoalkyl ether acetates such as ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate, propylene glycol monoalkyl ethers such as Propylene Glycol Monomethyl Ether (PGME) and propylene glycol monoethyl ether (PGEE), and propylene glycol monoalkyl ether acetates such as Propylene Glycol Monomethyl Ether Acetate (PGMEA) and propylene glycol monoethyl ether acetate.

These organic solvents may be used alone or in combination of 2 or more.

In a preferred embodiment, the organic solvent contained in the solvent (C) is selected from the group consisting of methanol, ethanol, isopropanol, tetrahydrofuran, propylene glycol monoethyl ether, benzene, acetone, methyl isobutyl ketone, cyclopentanone, cyclohexanone, and any combination thereof. (C) The organic solvent contained in the solvent is more preferably selected from the group consisting of methanol, ethanol, isopropanol, propylene glycol monoethyl ether, acetone, and any combination thereof, and further preferably methanol, ethanol, isopropanol, and propylene glycol monoethyl ether. When the organic solvent is a combination of two solvents, the volume ratio is preferably 20: 80-80: 20, more preferably 30: 70-70: 30, and further preferably 40: 60-60: 40.

In one embodiment of the present invention, the mass of the solvent (C) is 30 to 99 mass% (preferably 50 to 95 mass%, more preferably 80 to 95 mass%, and still more preferably 85 to 95 mass%) based on the mass of the substrate pattern filling composition.

When (A) the first solute, (B) the second solute and (C) the solvent have a boiling point of bp at one atmosphere_A、bp_BAnd bp_CThen, it satisfies bp_A＞bp_B＞bp_CIs one embodiment of the present invention. Further, (A) the first solute, (B) the second solute and (C) the solvent have a saturated vapor pressure vp at 25 ℃ and one atmospheric pressure_A、vp_BAnd vp_CWhen it is, vp is satisfied_A＜vp_B＜vp_CIs one embodiment of the present invention. Without being bound by theory, it is believed that by using a composition satisfying such a relationship, (C) the solvent is volatilized to form a film composed of solid components, and then (B) the second solute and (a) the first solute are sequentially vaporized when the composition is applied to the substrate pattern. It should be noted that these state changes are an overall trend, and need not be performed completely separately, but may be partially repeated. There may be ways in which the previously gasified material carries away the heat of gasification, so that the gasification as a whole can be staged. It is considered that (B) the second solute is first vaporized from the film, thereby avoiding rapid disappearance of the film and reducing interaction with the substrate pattern. It is considered that the low-density film of the first solute (a) remains in the film after the vaporization of the second solute (B). Since the low-density film has a low density, it is considered that the force applied to the substrate pattern when vaporized is reduced. Therefore, the component is preferably vaporized when left standing at room temperature (20 to 27 ℃ C., preferably 23 to 25 ℃ C.) for 180 seconds.

bp_AAnd/or bp_BPreferably 100 to 300 ℃, and more preferably 150 to 295 ℃. bp of bp_CPreferably 50 to 170 ℃, more preferably 50 to 150 ℃, and further preferably 60 to 140 ℃.

(D) A third solute, (E) a fourth solute

The substrate pattern filling composition of the present invention may further contain (D) a third solute. Further, (E) a fourth solute may be contained. These remain as solid components in the film formed from the substrate pattern filling composition filled in the substrate pattern. They are independently vaporized from the membrane.

(D) Specific examples of the third solute and the fourth solute (E) are the same as the specific examples of the first solute (a) and/or the second solute (B) described above.

Boiling of (D) a third solute and (E) a fourth soluteThe dots are bp_D、bp_ESaturated vapor pressure at 25 ℃ and 1 atm is vp_D、vp_EPreferably, bp is satisfied_C＜bp_E＜bp_D＜bp_B＜bp_A. Further, vp is satisfied_A＜vp_B＜vp_D＜vp_E＜vp_CAre also preferred. Without being bound by theory, it is believed that by satisfying this relationship, (E) the fourth solute, (D) the third solute, (B) the second solute, (a) the first solute are vaporized in order from the film formed from the composition.

The mass ratio of the first solute (A) to the third solute (D) is preferably 99:1 to 1:99 (more preferably 95:5 to 5:95, still more preferably 90:10 to 10:90, and still more preferably 80:20 to 20: 80). The mass ratio of the first solute (A) to the fourth solute (E) is preferably 99:1 to 1:99 (more preferably 95:5 to 5:95, still more preferably 90:10 to 10:90, and still more preferably 80:20 to 20: 80).

(F) Other additives

The substrate pattern filling composition according to the present invention may further comprise (F) other additives. (F) Other additives include surfactants, antibacterial agents, bactericides, preservatives, antifungal agents, acids or bases. (F) The other additives are preferably highly volatile. It is desirable that (F) the other additives are vaporized while (a) the first solute and (B) the second solute as solid components are vaporized in the process, or before and after.

The amount of the other additive (F) is 0 to 20 mass% (preferably 0 to 10 mass%, more preferably 0 to 5 mass%) relative to the total mass of the first solute (A) and the second solute (B). The absence (F) of other additives (0 mass%) is also a preferred embodiment of the present invention.

The surfactant which may be contained in the (F) other additive is expected to improve the coatability. Any surfactant may be used. Examples of the surfactant which can be used in the present invention include (F-1) anionic surfactants, (F-2) cationic surfactants or (F-3) nonionic surfactants. More specifically, (F-1) alkylsulfonic acid salts, alkylbenzenesulfonic acids, and alkylbenzenesulfonic acid salts, (F-2) dodecylpyridinium chloride, and dodecylmethylammonium chloride, (F-3) polyoxyethylene octyl ether, polyoxyethylene lauryl ether, and polyoxyethylene acetylene glycol ether are preferable. These surfactants are commercially available, for example, nonionic alkyl ether surfactants manufactured by japan emulsifier corporation, as exemplified by nonionic surfactants.

In addition, the substrate pattern filling composition according to the present invention may include an antibacterial agent, a bactericide, an antiseptic agent and/or an antifungal agent as (F) the other additive. These agents are used to prevent the growth of bacteria or fungus in the substrate pattern fill composition over time. Examples thereof include phenoxyethanol and alcohols such as isothiazolinone. Bestcide (trade name) sold by japan caokada corporation is a potent preservative, antifungal and fungicide. These agents do not generally affect the performance of the substrate pattern filling composition, and the content is generally 1 wt% or less, preferably 0.1 wt% or less, and more preferably 0.001 wt% or less, of the total mass of the substrate pattern filling composition.

In addition, the substrate pattern filling composition according to the present invention may include acids, bases as (F) other additives. The acid or alkali is used to adjust the pH of the treatment solution and to improve the solubility of the components. For the sake of clarity, in a substrate pattern filling composition, (F) the other additives are other compounds than the components of (a) to (E) described above.

The acid or base to be used may be arbitrarily selected within a range not impairing the effect of the present invention, and examples thereof include carboxylic acids, amines, and ammonium salts. These include fatty acids, aromatic carboxylic acids, primary amines, secondary amines, tertiary amines, ammonium compounds, which may be substituted with any substituent. More specifically, formic acid, acetic acid, propionic acid, benzoic acid, phthalic acid, salicylic acid, lactic acid, malic acid, citric acid, oxalic acid, malonic acid, succinic acid, fumaric acid, maleic acid, aconitic acid, glutaric acid, adipic acid, monoethanolamine, diethanolamine, triethanolamine, triisopropanolamine, tetramethylammonium, and the like are cited.

Method for forming substrate pattern

Hereinafter, a substrate pattern forming method according to an embodiment of the present invention will be described with reference to the accompanying drawings. The method for forming the substrate pattern may be arbitrarily selected from known methods such as dry etching. For example, non-patent document 1 and the like also describe such a method of forming a substrate pattern.

Various pretreatments may be combined with the substrate pattern forming method of the present invention.

Fig. 1 (a) shows the following modes: a carbon-coated film (also referred to as a C-coated film, a spin-on carbon film) layer 2 is formed on a substrate 1, a silicon-containing anti-reflection film (also referred to as a Si-ARC) layer 3 is formed thereon, and a resist pattern 4 is formed thereon.

The substrate to be used is not particularly limited, and examples thereof include a semiconductor substrate (e.g., a silicon wafer), and a glass substrate such as an LCD and a PDP. A conductive film, a wiring, a semiconductor, or the like may be formed over the substrate.

The carbon-coated film can be applied, pre-baked, and formed by a conventionally known method such as spin coating. Further, the film can be formed by a CVD (chemical vapor deposition) method or an ALD (atomic layer deposition) method.

The silicon-containing anti-reflective coating layer may be applied by spin coating, and may be pre-baked to form a film. The silicon-containing anti-reflection film layer can improve the cross-sectional shape and the exposure margin. Further, since the silicon-containing antireflection film layer is used as an etching mask, for example, an antireflection film layer having etching resistance is preferable.

The resist pattern can be formed by combining known methods. For example, patent document 3 discloses a method of manufacturing a semiconductor device.

The step of etching the underlying film (intermediate layer) using the resist pattern as a mask to form a mask may be performed in stages, or the substrate may be directly etched using the resist pattern as a mask. The etching of the intermediate layer may be dry etching or wet etching.

Fig. 1 (b) shows a state where the substrate is dry-etched to form the gap 5. The type of the dry etching gas is not particularly limited, and a freon gas is generally used. After dry etching, residue 6 (debris) remains between the patterns.

Fig. 1(c) shows a state where the substrate pattern is cleaned with the cleaning liquid 7. The cleaning liquid 7 can be applied by a known method, and examples thereof include coating, dropping and dipping. Any combination of these may be used. The residue 8 is removed by the cleaning process.

Fig. 1 (d) shows a state where the substrate pattern is filled with the substrate pattern filling composition 9 of the present invention. When the liquid in fig. 1(c) remains, the composition of the present invention is applied (preferably, applied, dropped, or impregnated). The coating method is not particularly limited, and for example, a method of spreading the composition by dripping while rotating the substrate at 1 to 500rpm on the surface of the substrate, a method of spreading the composition by leaving the substrate stationary and dripping the composition on the surface of the substrate and then rotating the substrate at 1 to 500rpm, a method of dipping the substrate, or supplying by spraying or spraying is performed. Among them, a method of dropping and spreading the composition on the surface of the substrate while rotating the substrate at 1 to 500rpm, a method of standing and dropping the substrate on the surface of the substrate and then rotating the substrate at 1 to 500rpm to spread the composition are preferable. At this time, at least a part of the liquid is replaced, and the composition is filled in the substrate pattern. In order to sufficiently exhibit the effects of the present invention, sufficient substitution is preferable.

After the above process, the substrate may be rotated at a speed of more than 500rpm and less than 5000 rpm. By this rotation, an excess of the organic solvent and water of the present composition is removed from the substrate, but at least a part of (a) the first solute and (B) the second solute remains. Since all of the composition does not disappear between the patterns, it is considered that the pattern collapse can be prevented.

Here, the following examples are given as one embodiment of the present invention. In the substrate pattern forming method of the present invention, the substrate pattern formed in advance may be washed with a washing liquid before applying (preferably coating) the substrate pattern filling composition, and the liquid present on the substrate may be replaced with the substrate pattern filling composition of the present invention. The substrate pattern formed in advance is in a state before the cleaning process, and a residue (debris or the like) may remain on the pattern surface. The liquid present on the substrate is, for example, a cleaning liquid. The cleaning may be performed in a plurality of steps, and for example, a cleaning solution (acid, alkali, etc.) for dissolving and removing inorganic substances may be applied, and then a cleaning solution (ion-exchanged water, organic solvent) having high compatibility with the substrate pattern filling composition of the present invention may be applied. Replacing the liquid present on the substrate means replacing the liquid present before applying the substrate pattern fill composition. Preferably, the liquid remaining in the substrate pattern is sufficiently replaced.

Fig. 1 (e) shows a state where the filled composition is removed and a pattern 10 is formed.

The composition may also be removed by heating, reduced pressure, air drying, standing, or a combination thereof. These removal methods may use any method as long as the pattern shape is not damaged. The heating time is not particularly limited, but is preferably 10 to 180 seconds, more preferably 10 to 120 seconds, and further preferably 10 to 90 seconds. The decompression time is not particularly limited, but is preferably 0.5 to 60 minutes, and more preferably 0.5 to 10 minutes. The pressure reduction can be controlled by using a dryer or an oil pump. Alternatively, air drying to remove the composition may be carried out by maintaining the pattern in an air stream. In this case, the air flow may be either positive or negative. In particular, the gas stream may be generated by gas injection. In this case, the gas to be used is not particularly limited, and air or the like may be used, but an inert gas is preferable. Specifically, argon, nitrogen, or the like is preferably used. The flow rate of the gas stream is not particularly limited and may be appropriately selected for removing the composition. In the removal of the composition, the humidity of the gas forming the atmosphere or the gas flow is preferably low, and for example, the humidity may be 10% or less, preferably 5% or less, more preferably 1% or less, and particularly preferably 0.1% or less.

The substrate pattern forming method of the present invention can suppress collapse rate even in a fine pattern. For example, a pillar (cylinder) having a thinner central portion than a bottom portion and/or a top portion is liable to collapse, but even if such a pillar pattern structure is employed, the collapse rate can be suppressed and cleaning can be performed.

The line-space structure pattern as a wall structure is considered to be less likely to collapse than the columnar pattern, but the collapse rate can be further reduced by using the substrate pattern forming method of the present invention.

Here, as shown in fig. 1 (e), the line width of the pattern formed on the substrate is x, and the length in the depth direction is y. The aspect ratio of the pattern is represented by y/x. The pattern to which the present invention is effectively applied has y of 0.01 to 6 μm or less, preferably 0.05 to 5 μm, and more preferably 0.1 to 3 μm. The aspect ratio is preferably 5 to 25, and more preferably 15 to 22.

Substrate

In the present invention, examples of the substrate include a semiconductor wafer, a glass substrate for a liquid crystal display device, a glass substrate for an organic EL display device, a glass substrate for a plasma display device, a substrate for an optical disk, a substrate for a magnetic disk, a substrate for an optical disk, a glass for a photomask, a substrate for a solar cell, and the like. The substrate may be a raw substrate (e.g., a die) or a processed substrate (e.g., a pattern substrate). The substrate may be constructed by laminating a plurality of layers. Preferably, the surface of the substrate is a semiconductor. The semiconductor may be composed of an oxide, a nitride, a metal, or any combination thereof. Preferably, the surface of the substrate is selected from the group consisting of Si, Ge, SiGe, and Si₃N₄、TaN、SiO₂、TiO₂、Al₂O₃、SiON、HfO₂、T₂O₅、HfSiO₄、Y₂O₃、GaN、TiN、TaN、Si₃N₄NbN, Cu, Ta, W, Hf, Al.

Device with a metal layer

Devices can be fabricated by further processing the substrates of the present invention. As the device, a semiconductor device, a liquid crystal display device, an organic EL display device, a plasma display device, and a solar cell device can be cited. The device is preferably a semiconductor. These processes may be performed by known methods. After forming the device, the substrate may be cut into chips, connected to a lead frame, and packaged with resin as necessary. An example of such a packaged product is a semiconductor.

The invention will be illustrated below using various embodiments. The mode of the invention is not limited to these examples.

EXAMPLES preparation example 1 of composition 1

1-adamantanamine as a first solute and camphor as a second solute were added to the IPA solvent in amounts of 10 mass%, respectively. The vessel was capped and stirred overnight to obtain a solution. The dissolution of the solute can be visually confirmed. The solution was filtered through a filter having a pore size of 0.1 μm to obtain example composition 1.

Examples 2 to 21 for the compositions 2 to 21 of examples and comparative examples 1 to 8 for the compositions 1 to 8 of comparative examples

Example compositions 2 to 21 and comparative example compositions 1 to 8 were obtained in the same manner as in preparation example 1, except that the solute, amount or solvent described in table 1 was changed. For each, it was visually confirmed that the solute was dissolved after stirring.

Evaluation of sublimation Property

The 300mm bare silicon wafer was inserted into a coating and developing machine RF3 (SOKUDO). 10cc of each composition was dropped on the wafer moved to the coating cup and spin-coated at a speed of 1,500rpm for 20 seconds. Thereafter, the coating cup was left standing and visually observed for a maximum of 120 seconds. The temperature in the coating cup is about 21 to 23 ℃.

The sublimability of each sample was evaluated according to the following evaluation criteria. The results are shown in Table 1.

A: the solid content in the composition formed a film, but it was confirmed that the film was vaporized and disappeared within 120 seconds.

B: the solid content in the composition formed a film, but it was confirmed that the film did not disappear after 120 seconds.

The sample wafer evaluated as B was further heated on a hot plate (100 ℃ C., 90 seconds) and visually observed. The sublimability was evaluated according to the following criteria.

B1: the disappearance of the film after heating was confirmed.

B2: it was confirmed that the film remained without disappearance after heating.

[ Table 1]

TABLE 1

The numerals in parentheses in the above table represent the mass% of the solute with respect to the whole composition.

Thereafter, the compositions were divided into a composition (group a) evaluated for sublimability a and a composition (group B) evaluated for sublimability B (B1, B2) and evaluated.

Evaluation of residual film (group A)

The samples evaluated for the above-mentioned sublimability were used.

The film thickness on the wafer was measured using an M-2000 ellipsometer (J.A Woollam). In ellipsometry measurement, only the residual film thickness was calculated by establishing a two-layer model in which the residual film and the native oxide film derived from this test were overlapped.

Each sample was evaluated for residual film according to the following evaluation criteria. The results are shown in Table 2.

A: the residual film thickness is less than 1 nm.

B: the residual film thickness is 1nm or more. Alternatively, the measurement light is scattered by the crystal grains and the residual film thickness cannot be measured.

Evaluation of collapse Rate (group A)

A 300mm silicon wafer (provided by interfacial Microelectronics Center (imec)) using a patterned columnar pattern. The pillars (cylinders) had a top diameter of about 31nm, a bottom diameter of about 67nm, and a height of about 590nm, and were patterned with pillars having a pitch of 80nm over the entire surface of the wafer.

To evaluate each composition, the above-described wafer was cut into about 5cm squares. The diced wafers were set on a MS-a150 spin coater (Mikasa). 2cc of each composition was dropped onto the wafer, and spin-coated at 1,000rpm for 20 seconds. The wafer was immediately removed and allowed to stand on a clean room lab bench for about 120 seconds. The temperature of the clean room was controlled at normal temperature (about 23 ℃).

After the above treatment, each wafer was observed from above with an SEM (SU8200, Hitachi High-Technologies). The area of the portion where the columnar pattern collapsed was divided by the total area observed to calculate the collapse rate. The results are shown in Table 2.

A: the collapse rate is less than 5%.

B: the collapse rate is more than 5%.

Comprehensive judgment

Both the residual film and the collapse rate are A as preferable. Otherwise as unsuitable. The results are shown in Table 2.

[ Table 2]

TABLE 2

The numerals in parentheses in the above tables represent the mass% of the solute with respect to the whole composition.

Evaluation of residual film due to sublimation (group B)

The samples evaluated for sublimation property were used. The measurement method and evaluation criteria were the same as those for the residual film of the group (A). The results are shown in Table 3.

(group B) evaluation of collapse Rate due to sublimation

A300 mm silicon wafer (imec) having a columnar pattern used for the evaluation of the collapse ratio of the patterned (group A) was used.

To evaluate each composition, the above-described wafer was cut into about 5cm squares. The diced wafer was set up on a MS-a150 spin coater. 2cc of each composition was dropped onto the wafer, and spin-coated at 1,000rpm for 20 seconds. The wafer was immediately removed and heated on a hot plate at 100 deg.C for 90 seconds. The measurement method and evaluation criteria after the treatment are the same as those of the collapse rate evaluation described above. The results are shown in Table 3.

Comprehensive judgment

Both the residual film and the collapse rate are A as preferable. Otherwise as unsuitable. The results are shown in Table 3.

[ Table 3]

TABLE 3

The numerals in parentheses in the above tables represent the mass% of the solute with respect to the whole composition.

Description of the symbols

1. Substrate

2. Carbon-coated film layer

3. Silicon-containing anti-reflection film layer

4. Resist pattern

5. Gap

6. Residue of the reaction

7. Cleaning liquid

8. Residue of the reaction

9. Substrate pattern filling composition according to the present invention

10. And (4) patterning.