Compositions and antireflective coatings for photolithography
14 claims: 10 independent, 4 dependent
- 1少なくとも下記の:A)式1: (式中、Raは、1つまたは複数の多重結合を含み、ただし、Raが、2つ以上の多重結合を含む場合、これらの多重結合は、共役配置にはなく;R1、R2、およびR3は、各々独立して、アルコキシル、ヒドロキシル、ハライド、OC(O)R、またはOC(O)OR(式中、Rは、アルキルまたは置換アルキルである)から選択される)から選択される化合物F1;および B)式2: (式中、Rbは、Hまたはアルキル、アルキレン、もしくはアルキリデンを含む飽和基から選択され;R4、R5、およびR6は、各々独立して、アルコキシル、ヒドロキシル、ハライド、OC(O)R、またはOC(O)OR(式中、Rは、アルキルまたは置換アルキルである)から選択される)から選択される化合物F2;および C)式3: (式中、Rcは2つ以上の多重結合を含み、これらの多重結合は、共役配置にあり;R7、R8、およびR9は、各々独立して、アルコキシル、ヒドロキシル、ハライド、OC(O)R、またはOC(O)OR(式中、Rは、アルキルまたは置換アルキルである)から選択される)から選択される化合物F3;および D)式4: (式中、R10、R11、R12、およびR13は、各々独立して、アルコキシル、ヒドロキシル、ハライド、OC(O)R、またはOC(O)OR(式中、Rは、アルキルまたは置換アルキルである)から選択される)から選択される化合物F4を含 み、化合物F1が、化合物F1、F2、F3およびF4の合計モルを基準として、12モルパーセントを超える量で存在する、 第一組成物。
- 2化合物F1、F2、F3およびF4の合計重量を基準として、Si5重量パーセント以上を含む、請求項1に記載の第一組成物。
- 3化合物F2と化合物F4の合計モル量が、化合物F1、F2、F3およびF4の合計モルを基準として、40モルパーセント以上である、請求項1または請求項2に記載の第一組成物。
- 4化合物F4が、化合物F1、F2、F3およびF4の合計モルを基準として、10モルパーセントを超える量で存在する、請求項1から4のいずれかに記載の第一組成物。
- 5化合物F4が、化合物F1、F2、F3およびF4の合計モルを基準として、65モルパーセント未満の量で存在する、請求項 1~4 のいずれかに記載の第一組成物。
- 6請求項 1~5 のいずれかに記載の第一組成物から形成されるプレポリマー。
- 7プレポリマー請求項 6 、および下記の:アミン含有化合物、ハライド含有化合物、塩酸塩、アンモニウム含有化合物、またはそれらの混合物のうちの少なくとも1つを含む第二組成物。
- 8請求項 7 に記載の第二組成物から形成される架橋組成物。
- 9請求項 1~8 のいずれかに記載の組成物から形成される少なくとも1つの成分を含む物品。
- 10請求項1~ 8 のいずれかに記載の組成物から形成される少なくとも1つの層を含む膜。
- 11ポリマーを含む第三組成物から形成される第二の層をさらに含む、請求項 10 に記載の膜。
- 12基板上でコーティングを形成する方法であって、少なくとも下記の:基板を準備すること、 基板上で下層を形成すること(下層は、少なくとも1つのポリマーを含む)、 下層の上に請求項1~ 5 のいずれかに記載の第一組成物または請求項 7 に記載の第二組成物を塗布すること、および 第一組成物または第二組成物を硬化させ、コーティングを形成することを含む方法。
- 13第一組成物または第二組成物の複数の層が、下層の上に塗布される、請求項 12 に記載の方法。
- 14コーティングが、反射防止層である、請求項 12 または請求項 13 に記載の方法。
Independent claims14
160 paragraphs, as filed
0001This application claims the benefit of US Provisional Application No. 61 / 537,098, filed September 21, 2011, which is incorporated herein by reference.
0002The present invention relates to compositions for use in microelectronic applications, in particular backside anti-reflective coating compositions (or "BARC"). The microelectronics industry continues to need microchips with smaller and clearer lithographic patterns. The problems faced by these developments today are the deterioration of the developed photoresist profile due to reflections at the interface between the photoresist layer and the substrate, the shorter exposure wavelengths, and sufficient etching resistance. Includes the need for a thin resist layer. Anti-reflective coatings can be used to address the above issues. One method of manufacturing anti-reflection coatings is by chemical vapor deposition (CVD), which is a costly process. It is necessary to simplify lithographic processing and avoid the costly vacuum coating of the antireflection layer. Therefore, there is a need for a composition for antireflection coating that has high etching selectivity with respect to the resist and can be formed by a spin coating process.
0003U.S. Patent Application Publication No. 2009/0148789 discloses silicon-containing organic coating compositions, in particular anti-reflection coating compositions containing chromophore moieties such as phenyl that are spaced apart from Si atoms (s). doing. This publication also discloses a silicon-containing underlayer composition that is formulated as a liquid (organic solvent) composition and in which at least one of the solvent components is a hydroxy group.
0004U.S. Patent Application Publication No. 2007/0185298 discloses a curable organic silicate composition used to form one or more layers in the manufacture of electronic devices. The composition comprises the following: (a) an alkoxysilane or acyloxysilane containing ethylenically unsaturated and having at least one group attached to a silicon atom; (b) containing an aromatic ring and a silicon atom. Alkoxysilane or acyloxysilane having at least one group attached to; (c) latent acid catalyst; and (d) optionally having at least one C1-C6 alkyl group attached to a silicon atom. Includes alkoxysilane or acyloxysilane.
0005US Pat. No. 5,621,034 states: (A) an organopolysiloxane resin having a hydroxyl group and / or an alkoxy group attached to a silicon atom; and (B) below: (B1) at least two carboxyl groups. A storage-stable composition comprising an aliphatic polycarboxylic acid having and (B2) a stabilizer selected from among carboxylic acid anhydrides of an aliphatic polycarboxylic acid having at least two carboxyl groups is disclosed.
0006WO 2009/088600 discloses a silsesquioxane resin that is useful in antireflection coatings, where the silsesquioxane resin is of the formula: (PhSiO (PhSiO (PhSiO).<sub>3-x) / 2</sub>(OR')<sub>x</sub>)<sub>m</sub>(HSiO (<sub>3-x) / 2</sub>(OR')<sub>x</sub>)<sub>n</sub>(MeSiO (<sub>3-x) / 2</sub>(OR')<sub>x</sub>)<sub>o o</sub>(RSiO (<sub>3-x) / 2</sub>(OR')<sub>x</sub>)<sub>p</sub>(R<sup>2</sup>SiO (<sub>3-x) / 2</sub>(OR')<sub>x</sub>)<sub>q</sub>Have. In this formula, Ph is a phenyl group, Me is a methyl group, R is selected from sulfur-containing organic functional groups, and R'is a hydrocarbon having a hydrogen atom or 1 to 4 carbon atoms. Group and R<sup>2</sup>Is selected from ester groups, polyether groups, and polyethylene oxide groups, where x has a value of 0, 1 or 2, m has a value of 0.01 to 0.97, and n has a value of 0.01 to 0.97. Has a value, o has a value of 0.01 to 0.97, p has a value of 0.01 to 0.97, q has a value of 0 to 0.96, m + n + o + p + q Is about 1.
0007U.S. Pat. No. 7,417,104 has the following: (A) Equation (1): R<sup>1</sup><sub>n</sub>-Si-R<sup>2</sup><sub>4-n</sub>Discloses a porous film-forming composition containing a polymer obtained by hydrolyzing and condensing hydrolyzable silane having. In this equation, R<sup>1</sup>Is a monovalent organic group or hydrogen, R<sup>2</sup>Is a hydrolyzable or hydroxyl group (n is an integer from 0 to 3), a hydrolyzate thereof or a partial condensate thereof, provided that at least one silicon compound is R.<sup>1</sup>Has an organic crosslinkable group as.
0008US Patent Application Publication No. 2010/0086872 discloses a "thermosetting metal oxide-containing film forming composition" for forming a metal oxide-containing film formed in a multilayer resist process used in lithography. ing. The "thermocurable metal oxide-containing film-forming composition" includes at least the following: (A) a metal oxide-containing compound obtained by hydrolyzing and condensing a hydrolyzable silicon compound and a hydrolyzable metal compound; (B) heat. Includes (C) monovalent, divalent or higher organic acids with 1-30 carbon atoms; (D) trihydric or higher alcohols; and (E) organic solvents.
0009U.S. Pat. No. 6,268,457 discloses an antireflection coating material for deep UV photolithography that includes one or more organic dyes incorporated within a spin-on glass material. Suitable dyes absorb strongly over the wavelength range around wavelengths below 260 nm, such as 248 nm and 193 nm, which may be used in photolithography. The method of producing a dyed spin-on glass material comprises mixing one or more organic dyes with an alkoxysilane reactant during the synthesis of the spin-on glass material.
0010US Patent Application Publication No. 2005/0277058 is a polymer containing organic solvents, cross-linking agents, and photoabsorbing groups obtained by hydrolyzing and condensing two or more types of silicon compounds, cross-linking groups, and non-cross-linking groups. The antireflection film forming composition containing the above is disclosed.
0011U.S. Patent Application Publication No. 2010/0210765 discloses a composition for forming a resist underlayer. The resist underlayer film forming composition comprises the following: a polymer having a silicon atom in the main chain; a compound having a polycyclic structure; and an organic solvent. Polycyclic compounds have at least two carboxyl groups as substituents; the two carboxyl groups individually combine with two adjacent carbon atoms to form a polycyclic structure; two carboxyls. Both groups have an end or exo configuration or a cis configuration. Polymers with silicon atoms in the main chain can be formed from a mixture of alkoxysilanes.
0012Additional compositions and / or other electronic applications for anti-reflective coatings are disclosed in the references below: US Pat. Nos. 7303785, 7736837, 5100503, US Patent Application Publication No. 2005/0031964, And No. 2009/0148789.
0013However, conventional silicon-containing BARC compositions in the art do not meet the optical properties and lithographic performance suitable for small critical dimension patterning (<100 nm). In addition, some conventional compositions contain expensive and / or unstable components. For example, some compositions typically contain free radicals as well as "Si-H-containing" compounds that react with hydroxyl-containing compounds such as alcohol and water. Some compositions contain organic dyes that increase the costs associated with producing such compositions. Some compositions contain expensive POSS (polyhedral oligomeric silsesquioxane ((RSiO1.5) 8). Some compositions may lead to patterning defects such as scum. Contains sun.
<p num="0014"><patcit num="1"><text>U.S. Patent Application Publication No. 2009/0148789</text></patcit><patcit num="2"><text>U.S. Patent Application Publication No. 2007/0185298</text></patcit><patcit num="3"><text>U.S. Pat. No. 5,621,034</text></patcit><patcit num="4"><text>International Publication No. WO 2009/088600</text></patcit><patcit num="5"><text>U.S. Pat. No. 7,417,104</text></patcit><patcit num="6"><text>U.S. Patent Application Publication No. 2010/0086872</text></patcit><patcit num="7"><text>U.S. Pat. No. 6,268,457</text></patcit><patcit num="8"><text>U.S. Patent Application Publication No. 2005/0277058</text></patcit><patcit num="9"><text>U.S. Patent Application Publication No. 2010/0210765</text></patcit><patcit num="10"><text>U.S. Pat. No. 7303785</text></patcit><patcit num="11"><text>U.S. Pat. No. 7736837</text></patcit><patcit num="12"><text>U.S. Pat. No. 5,100,503</text></patcit><patcit num="13"><text>U.S. Patent Application Publication No. 2005/0031964</text></patcit><patcit num="14"><text>U.S. Patent Application Publication No. 2007/0238052</text></patcit><patcit num="15"><text>U.S. Pat. No. 6,042,997</text></patcit><patcit num="16"><text>U.S. Pat. No. 5,492,793</text></patcit><patcit num="17"><text>U.S. Pat. No. 5,929,176</text></patcit><patcit num="18"><text>U.S. Pat. No. 6,090,526</text></patcit><patcit num="19"><text>U.S. Pat. No. 5,843,624</text></patcit><patcit num="20"><text>U.S. Pat. No. 6,048,664</text></patcit><patcit num="21"><text>U.S. Pat. No. 6,057,083</text></patcit><patcit num="22"><text>European Application Publication No. 01008913</text></patcit><patcit num="23"><text>European Application Publication No. 00930542</text></patcit><patcit num="24"><text>U.S. Pat. No. 6,048,662</text></patcit></p>
<p num="0015"> Therefore, there is still a need for compositions that can be used as anti-reflective layer compositions and to form smaller and clearer lithography patterns. Further compositions are needed that have high etching selectivity with respect to etching the resist layer. There is an additional need for cost-effective compositions that can be formed on the antireflection layer using a spin coating process. These and other needs have been met by the following inventions.</p>
<p num="0016"> The present invention is at least as follows: A) Equation 1:</p><p num="0017"><chemistry num="1"><img id="000002" he="35" wi="77" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the equation, Ra contains one or more multiple bonds (ie, double or triple bonds) that include C = C, CC, C = O, C = N, and CN. However, if Ra contains more than one multiple bond, these multiple bonds are not in the conjugated configuration; R1, R2, and R3 are independent of alkoxyl, hydroxyl, halide, etc. Compounds F1; and selected from OC (O) R, or OC (O) OR (where R is selected from alkyl or substituted alkyl). B) Equation 2:</p><p num="0018"><chemistry num="2"><img id="000003" he="35" wi="77" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, Rb is selected from saturated groups containing H or alkyl, alkylene, or alkylidene; R4, R5, and R6 are independently alkoxyl, hydroxyl, halide, OC (O) R, or OC. Compound F2; and compound selected from (O) OR (where R is selected from alkyl or substituted alkyl). C) Equation 3:</p><p num="0019"><chemistry num="3"><img id="000004" he="35" wi="83" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the equation, Rc contains two or more multiple bonds that include C = C, CC, C = O, C = N, and CN, and these multiple bonds are in a conjugated configuration; R7, R8, and R9 are each independently selected from alkoxyl, hydroxyl, halide, OC (O) R, or OC (O) OR (where R is alkyl or substituted alkyl in the formula). Compounds selected from F3; and D) Equation 4</p><p num="0020"><chemistry num="4"><img id="000005" he="41" wi="77" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, R10, R11, R12, and R13 are each independently alkoxyl, hydroxyl, halide, OC (O) R, or OC (O) OR (in the formula, R is alkyl or substituted alkyl. The first composition containing the compound F4 selected from) is provided.</p>
0021<figref num="1">A schematic diagram of a three-layer film structure on a silicon wafer is drawn.</figref><figref num="2">Below is a cross-sectional view of the line pattern generated after the lithography process, illustrating (a) a perfectly square pattern; and (b) a defect pattern with scum.</figref><figref num="3">It depicts a "top-down" SEM image of the wafer surface after the lithography process, which illustrates a complete pattern collapse.</figref><figref num="4">A "top-down" SEM image of the wafer surface after the lithography process, which illustrates the pattern collapse margin.</figref><figref num="5">It is an SEM image of a lithography pattern without scum (Example 16, groove 42 nm / pitch 84 nm).</figref><figref num="6">It is an SEM image of a lithography pattern with scum (Comparative Example G, groove 42 nm / pitch 84 nm).</figref>
0022As discussed above, the invention is at least as follows: A) Equation 1
0023<chemistry num="5"><img id="000006" he="34" wi="77" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the equation, Ra contains one or more multiple bonds that include C = C, CC, C = O, C = N, and CN, where Ra is more than one multiple bond. If they contain bonds, these multiple bonds are not in the conjugated configuration; R1, R2, and R3 are each independently selected from alkoxyl, hydroxyl, halide, OC (O) R, or OC (O) OR (where R is alkyl or substituted alkyl in the formula). Compounds selected from F1; and B) Equation 2
0024<chemistry num="6"><img id="000007" he="33" wi="77" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, Rb is selected from saturated groups containing H or alkyl, alkylene, or alkylidene; R4, R5, and R6 are each independently selected from alkoxyl, hydroxyl, halide, OC (O) R, or OC (O) OR (where R is alkyl or substituted alkyl in the formula). Compounds selected from F2; and C) Equation 3
0025<chemistry num="7"><img id="000008" he="34" wi="77" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the equation, Rc contains two or more multiple bonds that include C = C, CC, C = O, C = N, and CN, and these multiple bonds are in a conjugated configuration; R7, R8, and R9 are each independently selected from alkoxyl, hydroxyl, halide, OC (O) R, or OC (O) OR (where R is alkyl or substituted alkyl in the formula). Compounds selected from F3; and D) Equation 4
0026<chemistry num="8"><img id="000009" he="42" wi="89" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, R10, R11, R12, and R13 are each independently alkoxyl, hydroxyl, halide, OC (O) R, or OC (O) OR (in the formula, R is alkyl or substituted alkyl. The first composition containing the compound F4 selected from) is provided.
0027In one embodiment, the first composition comprises 5% by weight or more, 10% by weight or more, or 15% by weight or more of Si, based on the total weight of the compounds F1, F2, F3 and F4.
0028In one embodiment, the total molar amount of compound F2 and compound F4 is greater than or equal to 40 mole percent with respect to the total molar amount of compounds F1, F2, F3 and F4.
0029In one embodiment, the total molar amount of Compound F2 and Compound F4 is 85 mole percent or less, or 80 mole percent or less, based on the total moles of Compounds F1, F2, F3 and F4.
0030In one embodiment, compound F4 is present in an amount greater than 10 mole percent relative to the total mole of compounds F1, F2, F3 and F4.
0031In one embodiment, the molar ratio of F1 / F4 is 1/20 to 1/1, or 1/15 to 1/1, or 1/10 to 1/1.
0032In one embodiment, for the first composition, F1 ranges from 5 to 50 weight percent, or 10 to 30 weight percent; F2 ranges from 5 to 50 weight percent, or 10 to 40 weight percent. F3 is in the range of 2 to 20 weight percent, or 2 to 10 weight percent; F4 is in the range of 20 to 80 weight percent, or 30 to 80 weight percent. Each weight percentage is based on the weight of the first composition.
0033In one embodiment, for the first composition, compound F1 is 10 to 90 mole percent, further 15 to 90 mole percent, further 20 to 90 moles, relative to the total moles of compounds F1, F2, F3 and F4. It is present in amounts up to percent, and even from 25 to 90 mole percent.
0034In one embodiment, for the first composition, compound F1 is present in an amount greater than 10 mol percent, even greater than 12 mol percent, relative to the total mole of compounds F1, F2, F3 and F4.
0035In one embodiment, for the first composition, compound F4 is 10 to 65 mole percent, further 10 to 60 mole percent, further 10 to 55 moles, relative to the total moles of compounds F1, F2, F3 and F4. It is present in percent, and in amounts from 10 to 50 mole percent.
0036In one embodiment, for the first composition, compound F4 is present in an amount of less than 65 mole percent, even less than 60 mole percent, relative to the total mole of compounds F1, F2, F3 and F4.
0037The first composition may include a combination of two or more embodiments described herein.
0038The present invention also provides a prepolymer formed from the first composition. In a further embodiment, the prepolymer is formed by at least the following: hydrolyzing the first composition to form a hydrolyzed product, and condensing the hydrolyzed product.
0039In one embodiment, the prepolymer has a Mw of 1,000 to 20,000 g / mol, or 1,000 to 10,000 g / mol, or 1,000 to 5,000 g / mol, as determined by conventional GPC.
0040In one embodiment, the prepolymer has Mw / Mn from 1.1 to 6, 1.2 to 5, or 1.5 to 4.
0041The prepolymer of the present invention may include a combination of two or more embodiments described herein.
0042The present invention also provides a second composition comprising the prepolymer of the present invention and at least one of the following: amine-containing compounds, halide-containing compounds, hydrochlorides, ammonium-containing compounds, or mixtures thereof.
0043The second composition may include a combination of two or more embodiments described herein.
0044The present invention also provides a crosslinked composition formed from a second composition.
0045The present invention also provides articles containing at least one component formed from the compositions of the present invention.
0046The present invention also provides an article containing at least one component formed from the first composition.
0047The present invention also provides an article containing at least one component formed from the second composition.
0048The present invention also provides an article containing at least one component formed from the prepolymer of the present invention.
0049In one embodiment, the article is a membrane.
0050The present invention also provides a membrane containing at least one layer formed from the composition of the present invention. In a further embodiment, the membrane comprises at least two layers. In a further embodiment, the second layer is formed from a third composition comprising at least one polymer.
0051The present invention also provides a film comprising at least two layers, the at least one layer being an antireflection layer formed from the composition of the invention, such as the first composition or the second composition. In a further embodiment, the other layer is a photoresist layer.
0052The present invention also provides a film comprising at least two layers, the at least one layer being an antireflection layer formed from the first composition. In a further embodiment, the other layer is a photoresist layer.
0053The present invention also provides a film comprising at least two layers, the at least one layer being an antireflection layer formed from the second composition. In a further embodiment, the other layer is a photoresist layer.
0054Articles of the invention may include a combination of two or more embodiments described herein.
0055The membrane of the present invention may include a combination of two or more embodiments described herein.
0056The present invention is a method of forming a coating on a substrate, at least: Preparing the board, Forming a lower layer on the substrate (the lower layer contains at least one polymer), Applying the first composition of the present invention or the second composition of the present invention on the lower layer, and Also provided are methods comprising curing the first or second composition to form a coating.
0057In a further embodiment, the method comprises applying at least one composition comprising at least one photoresist polymer onto the coating.
0058In one embodiment, the first composition or the plurality of layers of the second composition are applied on top of the lower layer.
0059In one embodiment, the coating is an antireflection layer.
0060The present invention is a method of forming a coating on a substrate, at least: Preparing the board, Applying the first composition of the present invention or the second composition of the present invention on at least a part of the substrate or on one or more intermediate layers applied on the substrate, and Also provided are methods comprising curing the first or second composition to form a coating.
0061In a further embodiment, the method comprises applying at least one composition comprising at least one photoresist polymer onto the coating.
0062In one embodiment, the first composition or the plurality of layers of the second composition is applied on at least a portion of the substrate or on one or more intermediate layers applied on the substrate. To.
0063In one embodiment, the coating is an antireflection layer.
0064The methods of the invention may include a combination of two or more embodiments described herein.
0065Compounds F1 ~ F4 Compounds F1, F2, F3 and F4 are listed below.
0066A) Equation 1:
0067<chemistry num="9"><img id="000010" he="33" wi="77" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the equation, Ra contains one or more multiple bonds comprising C = C, CC, C = O, C = N, and CN, where Ra is more than one multiple bond. If they contain bonds, these multiple bonds are not in the conjugated configuration; R1, R2, and R3 are each independent, alkoxyl, hydroxyl, halide, OC (O) R, or OC (O) OR (formula). Among them, R is a compound F1 selected from (selected from alkyl or substituted alkyl). In a further embodiment, R is alkyl.
0068In one embodiment, Ra comprises one or more of an alkenyl group, an alkynyl group, an imide, a nitrile, a ketone, an ester, an amide, or a carbonate and comprises 2 to 10 carbon atoms; R1, R2. , And R3 are independently OH, OR, or OC (O) R (in the equation, R is C.<sub>1</sub>~ C<sub>10</sub>Alkyl or C<sub>1</sub>~ C<sub>10</sub>(Substituted alkyl) is selected.
0069In one embodiment, Ra comprises one or more of an alkenyl group, an alkynyl group, an imide, a nitrile, a ketone, an ester, an amide, or a carbonate and comprises 2 to 10 carbon atoms; R1, R2. , And R3 are independently OH, OR, or OC (O) R (in the equation, R is C.<sub>1</sub>~ C<sub>10</sub>(Alkyl) is selected.
0070In one embodiment, Ra is selected from vinyl, allyl, propenyl, butenyl, acetoxyl, cyanoethyl, acetoethyl, or acetamidopropyl; R1, R2, and R3 are each OR (in the formula, each R is independent). , Methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, or 2-butyl).
0071In one embodiment, compound F1 is selected from vinyltrimethoxysilane or vinyltriethoxysilane.
0072<chemistry num="10"><img id="000011" he="25" wi="127" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
0073B) Equation 2:
0074<chemistry num="11"><img id="000012" he="33" wi="77" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, Rb is selected from saturated groups containing H or alkyl, alkylene, or alkylidene; R4, R5, and R6 are independently alkoxyl, hydroxyl, halide, OC (O) R, or OC. Compound F2 selected from (O) OR (where R is selected from alkyl or substituted alkyl). In a further embodiment, R is alkyl.
0075In one embodiment, Rb is selected from saturated groups containing alkyl, alkylene, or alkylidene; R4, R5, and R6 are each independently of alkoxyl, hydroxyl, halide, OC (O) R, or OC ( O) Selected from OR (where R is alkyl or substituted alkyl). In a further embodiment, R is alkyl.
0076In one embodiment, Rb is a substituted or unsubstituted C.<sub>1</sub>~ C<sub>10</sub>Cyclic alkyl, substituted or unsubstituted C<sub>1</sub>~ C<sub>10</sub>Acyclic alkyl, substituted or unsubstituted C<sub>1</sub>~ C<sub>10</sub>Cyclic alkylene, substituted or unsubstituted C<sub>1</sub>~ C<sub>10</sub>Acyclic alkylene, substituted or unsubstituted C<sub>1</sub>~ C<sub>10</sub>Cyclic alkylidene, substituted or unsubstituted C<sub>1</sub>~ C<sub>10</sub>Acyclic alkylidene, or H; or unsubstituted C<sub>1</sub>~ C<sub>10</sub>Cyclic alkyl, unsubstituted C<sub>1</sub>~ C<sub>10</sub>Acyclic alkyl, unsubstituted C<sub>1</sub>~ C<sub>10</sub>Cyclic alkylene, unsubstituted C<sub>1</sub>~ C<sub>10</sub>Acyclic alkylene, unsubstituted C<sub>1</sub>~ C<sub>10</sub>Cyclic alkylidene, unsubstituted C<sub>1</sub>~ C<sub>10</sub>Acyclic alkylidene, or H; or unsubstituted C<sub>1</sub>~ C<sub>10</sub>Cyclic alkyl, unsubstituted C<sub>1</sub>~ C<sub>10</sub>Acyclic alkyl, or H; or unsubstituted C<sub>1</sub>~ C<sub>10</sub>Cyclic alkyl or unsubstituted C<sub>1</sub>~ C<sub>10</sub>Acyclic alkyl; or unsubstituted C<sub>1</sub>~ C<sub>10</sub>It is a saturated group containing acyclic alkyl; R4, R5, and R6 are independently OH, OR, or OC (O) R (in the equation, R is C.<sub>1</sub>~ C<sub>10</sub>Alkyl or C<sub>1</sub>~ C<sub>10</sub>(Substituted alkyl) is selected. In a further embodiment, R is C<sub>1</sub>~ C<sub>10</sub>It is alkyl.
0077In one embodiment, Rb is selected from methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, or 2-butyl; R4, R5, and R6 are each OR (in the formula, each R). Is independently selected from methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, or 2-butyl).
0078In one embodiment, compound F2 is selected from methyltrimethoxysilane or methyltriethoxysilane.
0079<chemistry num="12"><img id="000013" he="26" wi="127" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
0080C) Equation 3:
0081<chemistry num="13"><img id="000014" he="37" wi="77" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the equation, Rc contains two or more multiple bonds that include C = C, CC, C = O, C = N, and CN, and these multiple bonds are in a conjugated configuration; R7, R8, and R9 are each independently selected from alkoxyl, hydroxyl, halide, OC (O) R, or OC (O) OR (where R is alkyl or substituted alkyl in the formula). Compound F3 selected from. In a further embodiment, R is alkyl.
0082In one embodiment, Rc is an aryl or substituted aryl, a conjugated diene or conjugated triene, a conjugated diketone, a conjugated keto-ester, an α, β-unsaturated ester, an α, β-unsaturated ketone, a nitrile conjugated to an alkene. Includes, ketone-conjugated nitriles, ester-conjugated nitriles, alkene-conjugated alkynes, ketone-conjugated alkynes, or ester-conjugated alkynes; R7, R8, and R9 are independently OH, OR, or OC (O) R (in the equation, R is C.<sub>1</sub>~ C<sub>10</sub>Alkyl or C<sub>1</sub>~ C<sub>10</sub>(Substituted alkyl) is selected. In a further embodiment, R is C<sub>1</sub>~ C<sub>10</sub>It is alkyl.
0083In one embodiment, Rc is a phenyl group, a naphthyl group, an anthracene group, a phenanthrene group, a fluorene group, a pyridine group, a quinoline group, an imidazole group, a benzimidazole group, an indole group, a carbazole group, a furan group, a benzofuran group, a dibenzofuran group. , Includes acryloxyl group, acrylamide group, methacryloxil group, or methacrylamide group; R7, R8, and R9 are each OR (in the formula, each R is independently selected from methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, or 2-butyl). is there.
0084In one embodiment, compound F3 is selected from phenyltrimethoxysilane or phenyltriethoxysilane.
0085<chemistry num="14"><img id="000015" he="29" wi="153" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
0086D) Equation 4:
0087<chemistry num="15"><img id="000016" he="41" wi="77" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>(In the formula, R10, R11, R12, and R13 are each independently alkoxyl, hydroxyl, halide, OC (O) R, or OC (O) OR (in the formula, R is alkyl or substituted alkyl. ) To be selected from) compound F4. In a further embodiment, R is alkyl.
0088In one embodiment, R10, R11, R12, and R13 are independently OH, OR, or OC (O) R (in the formula, R is C).<sub>1</sub>~ C<sub>10</sub>Alkyl or C<sub>1</sub>~ C<sub>10</sub>(Substituted alkyl) is selected. In a further embodiment, R is C<sub>1</sub>~ C<sub>10</sub>It is alkyl.
0089In one embodiment, R10, R11, R12, and R13 are OR (in the formula, each R is independently methyl, ethyl, n-propyl, 2-propyl, n-butyl, isobutyl, or 2-butyl. Is selected from).
0090In one embodiment, compound F4 is selected from tetramethyl orthosilicate or tetraethyl orthosilicate.
0091<chemistry num="16"><img id="000017" he="31" wi="127" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
0092Three-layer coating A three-layer coating, eg, a three-layer resist, is typically (a) a curable underlayer composition on a substrate; (b) a hardmask composition applied over the curable composition (eg, the present specification). A hardmask layer formed from the compositions of the invention described in the book); and (c) a photoresist composition layer applied onto the hardmask composition. The substrate is suitable for any substrate used in processes involving photoresists. For example, the substrate may be silicon, silicon dioxide or aluminum-aluminum oxide microelectronic wafers. Gallium arsenide, silicon carbide, ceramic, quartz or copper substrates may also be used. Substrates for liquid crystal displays or other flat panel display applications, such as glass substrates, substrates coated with indium tin oxide, and the like are also suitable. Substrates for optical and optical-electronic devices (eg, waveguides) can also be used. Coating compositions and lytic processes are described in US Patent Application Publication No. 2007/0238052 and US Patent Application Publication No. 2009/0148789, each of which is incorporated herein by reference.
0093Various photoresists may be used in combination (ie, overcoated) with the coating compositions of the present invention. Preferred photoresists are chemically amplified resists, especially deblocking in the presence of photogenerated acids, such as one or more photoacid generator compounds and photoacid-labile esters, acetals, ketals or other units. Includes a positive-acting photoresist or a negative-acting photoresist containing a resin component containing a unit that undergoes a reaction or cleavage reaction.
0094Negative-acting photoresists, such as resists that crosslink (ie, cure or harden) upon exposure to activated irradiation, can also be used with the coating compositions of the present invention. Preferred photoresists for use with the coating compositions of the present invention are relatively short wavelength irradiations, such as irradiations with wavelengths less than 300 nm, such as about 248 nm, or wavelengths less than 260 nm, or wavelengths less than about 200 nm, such as 193 nm. It may be imaged by the irradiation that it has.
0095Suitable photoresists contain an amount of photoacid generator compound and one or more resins that are effective for imaging. Suitable resins include i) phenolic resins containing acid-labile groups (see, eg, US Pat. Nos. 6,042,997 and 5,492,793); ii) polymers described in US Pat. No. 6,042,997. , Vinyl phenol, optionally substituted vinyl phenyl (eg, styrene) containing neither hydroxyl ring substituents nor carboxyl ring substituents, and polymerization of alkyl acrylates such as the deblocking group described in Polymer i) above. Polymers containing the same units; and iii) Polymers containing repeating units containing acetal or ketal moieties that should react with photoacids and optionally aromatic repeating units such as phenyl or phenolic groups (as such). Polymers have been described in US Pat. Nos. 5,929,176 and 6,090,526), but are not limited thereto.
0096The additional resin is substantially or completely free of phenyl groups and other aromatic groups and can provide a chemically amplified resist that is particularly suitable for imaging at wavelengths below 200 nm, such as 193 nm. Including. Preferred resins in this class are i) non-aromatic cyclic olefins (intracyclic double bonds) such as optionally substituted norbornene, such as the polymers described in US Pat. Nos. 5,843,624 and 6,048,664. Polymers containing polymerized units of; ii) For example, t-butyl acrylate, t-butyl methacrylate, methyl adamantyl acrylate, methyl adamantyl methacrylate, and other acyclic alkyl acrylates and alicyclic acrylates. Polymers containing alkyl acrylate units (such polymers have been described in US Pat. Nos. 6,057,083; European Application Publication Nos. 01008913 and 00930542), and iii) European Application Publication No. 01008913 and US Patent No. Includes polymerized anhydride units, in particular polymers containing polymerized maleic anhydride and / or itaconic anhydride units, as disclosed in 6,048,662.
0097Other resins contain repeating units containing heteroatoms, in particular oxygen and / or sulfur (but non-anhydrides, ie, units containing no carbonyl ring atom), and virtually any aromatic unit. Alternatively, it includes a resin that is preferably not completely contained. The heteroaliphatic unit is preferably condensed with the resin backbone, and the resin is provided by polymerization of the anhydride unit, such as that provided by polymerization of a norbolene group and / or maleic anhydride or itaconic anhydride. It is more preferable to include such a condensed carbon alicyclic unit. Further, the resin (fluoropolymer) containing fluorine substitution may be provided by, for example, polymerization of a fluorinated aromatic group such as tetrafluoroethylene or a fluorostyrene compound.
0098Definition The term "composition" includes, as used herein, a material containing the composition, as well as a mixture of reaction and degradation products formed from the material of the composition.
0099The term "polymer" refers to polymer compounds prepared by polymerizing monomers, whether of the same type or different types, as used herein. Therefore, the general term polymer is used to refer to the term homopolymer, a polymer prepared from only one type of monomer, with the understanding that trace amounts of impurities may be incorporated into the polymer structure. ) And the term interpolymer as defined later herein.
0100The term "interpolymer" refers to a polymer prepared by the polymerization of at least two different types of monomers, as used herein. The general term interpolymer includes copolymers (used to refer to polymers prepared from two different monomers) and polymers prepared from three or more different types of monomers.
0101The term "prepolymer", as used herein, is used, for example, from about 500 g / mol to 100,000, g / mol, preferably from about 500 to 50,000 g / mol (described below). As determined by conventional GPC), it refers to a polymer with a molecular weight of Mw (weight average).
0102The term "multiple bond" as used herein may refer to a double bond or a triple bond.
0103The term "coupled configuration" as used herein refers to two multiple bonds separated by a single single bond in an alternating pattern (eg, "double bond-single bond-double bond" or "double bond-single bond-double bond". Refers to the arrangement of multiple bonds that occur in a compound that form a "triple bond-single bond-double bond" or "double bond-single bond-triple bond"). In a conjugated configuration, the multiple bond may independently be a double bond or a triple bond. Two or more alternating patterns may be present in the compound with the conjugate arrangement of the bonds. Examples of compounds with conjugated bonds are benzene, 1,4-butadiene, furan, acrylonitrile, and acrylic acid.
0104<chemistry num="17"><img id="000018" he="25" wi="153" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></chemistry>
0105The term "amine-containing compound" as used herein refers to at least one, preferably one amine group (eg, primary, secondary or tertiary amines (NH).<sub>2</sub>Or refers to an organic compound containing NH or N)).
0106The term "halide-containing compound", as used herein, is an organic compound containing at least one, preferably one, halide group (eg, Cl, Br, F, preferably Cl). Point to.
0107The terms "include," "include," "have," and their derivatives exclude the presence of any additional ingredients, steps, and procedures, whether or not they are specifically disclosed. Not intended to be. To avoid any doubt, all compositions claimed through the use of the term "contains", whether polymer or otherwise, any additional addition unless otherwise stated. Agents, adjuvants and compounds may also be included. In contrast, the term "becomes essential" excludes any other ingredients, steps, and procedures from the scope of any subsequent detail, except those that are not essential to operability. The term "consisting of" excludes any component, step, or procedure that is neither specifically described nor listed.
0108Test method GPC The molecular weight of the prepolymer was monitored by gel permeation chromatography (GPC), also known as size exclusion chromatography (SEC). The instrument was fitted with a set of columns suitable for measuring molecular weight in the range of about 500 g / mol to at least about 100,000 g / mol, relative to polystyrene calibration standards. Two 8 mm diameter x 300 mm long SHODEX LF-804 GPC columns available from a set of consecutive Thomson Instrument Co. were particularly effective. The mobile phase was tetrahydrofuran and pumped at a rate of 1 mL / min. A refractive index detector was also attached to the device. Calibration was performed using polystyrene standards available from Polymer Standards Service GmbH, Mainz, Germany. Mn, Mw, and MWD were calculated using the "GPC-Add-on" for ChemStation software available from Agilent Technologies, Inc.
0109SEM Both top-down images and cross-sectional images were measured with Hitachi CG4000 SEM (Hitachi High Technologies America, Inc.). Top-down measurements are made across the imaging wafer. The cross section is obtained by cutting the wafer through the features of interest and sputter coating the wafer section with a thin layer of gold or iridium.
0110Experimental section The materials used in the present invention are obtained from commercial sources and used as received. Abbreviations and raw material sources VTMS: Vinyl Trimethoxysilane (Sigma Aldrich, Dow Corning) MTMS: Methyltrimethoxysilane (Sigma Aldrich, Dow Corning) PTMS: Phenyltrimethoxysilane (Sigma Aldrich, Dow Corning) TEOS: Tetraethyl orthosilicate (Sigma Aldrich, Dow Corning) GlyTMS: Glysidexylpropyltrimethoxysilane (Sigma Aldrich, Dow Corning, Gelest) PGMEA: Propylene Glycol Monomethyl Ether Acetate (DOWANOL PMA, The Dow Chemical Company) BTEAC: benzyltriethylammonium chloride (Sigma Aldrich) Is.
0111A 3N aqueous acetic acid solution was prepared in the laboratory. Glacial acetic acid was supplied by JT Baker.
01120.1N aqueous hydrochloric acid was prepared in the laboratory. Concentrated hydrochloric acid was supplied by Fisher.
0113Table 1 lists the different first compositions used in the present invention. The amount is in mole percent with respect to the total number of moles added to prepare the composition.
0114<tables num="1"><img id="000019" he="95" wi="153" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>
0115Different prepolymers were synthesized using the above compositions as shown in Tables 2A and 2B. The detailed synthetic process of the prepolymer is described in the paragraph following Table 2B.
0116<tables num="2"><img id="000020" he="48" wi="153" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>
0117Synthesis of prepolymers of the present invention and comparative prepolymers Prepolymer 1 A three-necked round-bottomed flask equipped with a mechanical stirrer and a short-path distillation apparatus was charged with glacial acetic acid (0.52 mL) and HPLC grade submicron filtered water (20.52 mL) to form acetic acid / aqueous solution. In a plastic syringe equipped with a transfer line, phenyltrimethoxysilane (6.16 g, 31.1 mmol), methyltrimethoxysilane (21.64 g, 158.8 mmol), vinyltrimethoxysilane (7.68 g, 51.8 mmol), tetraethyl orthosilicate (21.58 mmol). A premixed solution of g, 103.6 mmol), and PGMEA (58.33 mL) was charged. The alkoxysilane monomer / PGMEA mixture was added dropwise to acetic acid / aqueous solution over 1 hour using a syringe pump. After the addition, the syringe transfer line was removed from the round bottom flask inlet and replaced with a thermocouple mounted within the glass joint to monitor the internal reaction temperature. The reaction mixture was stirred at room temperature for 10 minutes. The flask was then placed in a temperature controlled oil bath and the bath temperature was set to reach a temperature of 100 ° C. The condensation reaction proceeded in a nitrogen atmosphere while collecting alcohol and water by distillation. The reaction mixture was heated for 2 hours and 25 minutes. The concentrated reaction mixture was then diluted with PGMEA (42 mL) to an approximately 20 wt% solid to a final weight of 127.4 g. The solution was filtered through a 0.2 μm PTFE membrane filter.
0118The solid concentration was measured by drying 1 g of the sample in an oven at 110 ° C. The molecular weight was determined by GPC: Mw, 4152 g / mol; Mn, 1414 g / mol; MWD, 2.94.
0119Prepolymer 2 Phenyltrimethoxysilane (6.16 g, 31.1 mmol), methyltrimethoxysilane (21.64 g, 158.8 mmol), vinyltrimethoxysilane (7.68 g) in a three-necked round-bottomed flask equipped with a mechanical stirrer and a short-path distiller. , 51.8 mmol), tetraethyl orthosilicate (21.58 g, 103.6 mmol), and PGMEA (58.33 mL) were charged with a premixed solution. A plastic syringe equipped with a transfer line was charged with glacial acetic acid (0.52 mL) and HPLC grade submicron filtered water (27.98 mL). Acetic acid / aqueous solution was added to the alkoxysilane monomer / PGMEA mixture over 30 minutes using a syringe pump. After the addition, the syringe transfer line was removed from the round bottom flask inlet and replaced with a thermocouple mounted within the glass joint to monitor the internal reaction temperature. The flask was placed in a temperature controlled oil bath and the bath temperature was set to reach a temperature of 100 ° C. The condensation reaction proceeded in a nitrogen atmosphere while collecting alcohol and water by distillation. The reaction mixture was heated for 2.5 hours. The concentrated reaction mixture was then diluted with PGMEA (42 mL) to an approximately 20 wt% solid to a final weight of 127 g. The solution was filtered through a 0.2 μm PTFE membrane filter. The solid concentration was measured by drying 1 g of the sample in an oven at 110 ° C. The molecular weight was determined by GPC: Mw, 4627 g / mol; Mn, 1709 G / mol; PDI, 2.71.
0120Prepolymer 3 A 250 mL three-necked round-bottomed flask equipped with a magnetic stirrer and a short-path distillation apparatus was charged with 3N acetic acid (34.21 g). Phenyltrimethoxysilane (8.82 g), methyltrimethoxysilane (17.49 g), vinyltrimethoxysilane (10.96 g), tetraethyl orthosilicate (51.36 g), and PGMEA (82 mL) in a plastic syringe with a transfer line. The premixed solution was charged. The monomer solution was slowly added to the reaction flask using a syringe pump. One hour after the start of monomer addition, the flask was placed in a temperature controlled oil bath and the bath temperature was set to 100 ° C. After 3 hours, the bath temperature was raised to 110 ° C and kept at this temperature until the temperature in the reaction mixture reached 90 ° C. The oil bath was then removed to allow the polymer solution to cool. A second aliquot of PGMEA was added to prepare the polymer solution to a 20 wt% solid. The solid content of the polymer solution was determined by heating a sample of the polymer solution in an oven at 145 ° C for 1 hour. The molecular weight of the polymer was determined by GPC: Mw 3083 g / mol; Mn 1396 g / mol; MWD 2.21.
0121Prepolymer 4 A 500 mL three-necked round-bottom flask equipped with a magnetic stirrer and a Dean-Stark apparatus was charged with glacial acetic acid (13.33 g) and water (59.98 g). Phenyltrimethoxysilane (18.86g), methyltrimethoxysilane (37.41g), vinyltrimethoxysilane (23.48g), tetraethyl orthosilicate (110.04g), and PGMEA (175.07g) in a plastic syringe with a transfer line. Was charged with the premixed solution of. The monomer solution was added to the reaction flask over 1 hour using a syringe pump. The flask was placed in a temperature controlled oil bath set at 100 ° C and kept at that temperature for 1 hour. Distillate collection started. The bath temperature was raised to 110 ° C and kept at this temperature until the reaction temperature reached 90 ° C, at which point the heating bath was removed and the polymer solution was cooled. A second aliquot of PGMEA was added to prepare the polymer solution to a 20 wt% solid. The solid content of the polymer solution was determined by heating a sample of the polymer solution in an oven at 145 ° C for 1 hour. The molecular weight of the polymer was determined by GPC: Mw 2443 g / mol; Mn 1419 g / mol; MWD 1.72.
0122Prepolymer 5 A 250 mL three-necked round-bottomed flask equipped with a magnetic stirrer and a short-path distillation apparatus was charged with 3N acetic acid (34.5 g). Phenyltrimethoxysilane (8.81 g), methyltrimethoxysilane (17.46 g), vinyltrimethoxysilane (10.95 g), tetraethyl orthosilicate (51.36 g), and PGMEA (82 mL) in a plastic syringe with a transfer line. The premixed solution was charged. The monomer solution was slowly added to the reaction flask using a syringe pump. One hour after the start of monomer addition, the flask was placed in a temperature controlled oil bath and the bath temperature was set to 100 ° C. After 3 hours, the bath temperature was raised to 110 ° C and kept at this temperature until the reaction temperature reached 90 ° C, at which point the oil bath was removed and the polymer solution was cooled. A second aliquot of PGMEA was added to prepare the polymer solution to a 20 wt% solid. The solid content of the polymer solution was determined by heating a sample of the polymer solution in an oven at 145 ° C for 1 hour. The molecular weight of the polymer was determined by GPC: Mw 2928 g / mol.
0123Prepolymer 6 Vinyl trimethoxysilane (11.1 g), phenyltrimethoxysilane (9 g), methyltrimethoxysilane (31.3 g), tetraethyl orthosilicate (31.1 g), and PGMEA (65 g) were mixed and added to a glass syringe. A 500 mL three-necked round bottom flask was charged with 3N acetic acid (23.9 g). The inside of the flask was mixed with an overhead stirrer. The silane / solvent blend was added to the flask at room temperature using a syringe pump and the total addition time was 70 minutes. After the addition of silane, the Dean-Stark trap and nitrogen line were connected to the flask. The flask was placed in an oil bath, the bath was heated to 100 ° C., and the distillate was collected in a Dean-Stark trap. After collecting the distillate for 60 minutes, PGMEA (40 g) was added slowly to the flask. The oil bath was heated to 125 ° C. and continued for an additional 70 minutes, still collecting the distillate. A total of 57.8 g of distillate was collected. The flask was removed from the heat and the Dean-Stark trap was removed. The weight average molecular weight was determined by GPC to be 2590 g / mol. The flask was returned to the oil bath at 125 ° C. After 30 minutes at 125 ° C, the sample was taken from the flask and the weight average molecular weight was determined by GPC to be about 3790 g / mol. Heating at 125 ° C was continued for an additional 30 minutes. The flask was removed from the oil bath. The weight average molecular weight was determined by GPC to be 5040 g / mol. The concentration of the obtained siloxane polymer solution was 23.46 wt% based on the weight of the solution.
0124Prepolymer 7 Vinyl trimethoxysilane (11.1 g), phenyltrimethoxysilane (9 g), methyltrimethoxysilane (27.9 g), tetraethyl orthosilicate (36.4 g), and PGMEA (65 g) were mixed and added to a glass syringe. 3N acetic acid (24.1 g) was charged into a 500 mL three-necked round bottom flask. The inside of the flask was mixed with an overhead stirrer. The silane / solvent blend was added to the flask at room temperature using a syringe pump and the total addition time was 60 minutes. After the addition of silane, the Dean-Stark trap and nitrogen line were connected to the flask. The flask was placed in an oil bath heated to 100 ° C. and the distillate was collected in a Dean-Stark trap for 60 minutes. PGMEA (40 g) was then added slowly to the flask. The oil bath was heated to 125 ° C. and continued for an additional 60 minutes, still collecting the distillate. A total of 55.1 g of distillate was collected. The flask was removed from the heat and the Dean-Stark trap was removed. The weight average molecular weight was determined by GPC to be 3770 g / mol. The flask was returned to the oil bath at 125 ° C. After 15 minutes at 125 ° C, the flask was removed from the oil bath and cooled. The weight average molecular weight was determined by GPC to be approximately 4505 g / mol. The flask was returned to the oil bath at 125 ° C. and heating was continued for an additional 16 minutes. The flask was removed from the oil bath. The weight average molecular weight was determined by GPC to be 5620 g / mol. The concentration of the obtained siloxane polymer solution was 27.29 wt% based on the weight of the solution.
0125Prepolymer 8 Vinyl trimethoxysilane (11.1 g), phenyltrimethoxysilane (9 g), methyltrimethoxysilane (24.5 g), tetraethyl orthosilicate (41.6 g), and PGMEA (65 g) were mixed and added to a glass syringe. 3N acetic acid (24.3 g) was charged into a 500 mL three-necked round bottom flask. The inside of the flask was mixed with an overhead stirrer. The silane / solvent blend was added to the flask at room temperature using a syringe pump and the total addition time was 62 minutes. After the addition of silane, the Dean-Stark trap and nitrogen line were connected to the flask. The flask was placed in an oil bath heated to 100 ° C. and the distillate was collected in a Dean-Stark trap. After collecting the distillate for 51 minutes, PGMEA (50 g) was added slowly to the flask. The oil bath was heated to 125 ° C. for an additional 45 minutes, still collecting the distillate. A total of 52.5 g of distillate was collected. The flask was removed from the heat and the Dean-Stark trap was removed. The weight average molecular weight was determined by GPC to be 3020 g / mol. The flask was returned to the oil bath at 125 ° C. After 16 minutes at 125 ° C, the flask was removed from the oil bath and allowed to cool. The weight average molecular weight was determined by GPC to be approximately 3675 g / mol. The flask was returned to the oil bath at 125 ° C. and heating was continued for an additional 30 minutes. The flask was removed from the oil bath. The weight average molecular weight was determined by GPC to be 4960 g / mol. The flask was returned to the oil bath at 125 ° C. and heating was continued for an additional 15 minutes. The flask was removed from the oil bath. The weight average molecular weight was determined by GPC to be 5925 g / mol. The concentration of the obtained siloxane polymer solution was 23.01 wt%.
0126Prepolymer A Vinyl trimethoxysilane (65.9 g), phenyl trimethoxysilane (5.9 g), and methyl trimethoxysilane (3.4 g) were mixed and added to a glass syringe. A 500 mL three-necked round bottom flask was charged with 3N acetic acid (27 g). The inside of the flask was mixed with an overhead stirrer. Silane was added to the flask using a syringe pump and the total addition time was 45 minutes. After the addition of silane, the Dean-Stark trap and nitrogen line were connected to the flask. The flask was placed in an oil bath heated to 100 ° C. After collecting the distillate in the Dean-Stark trap for 45 minutes, PGMEA (75 g) was slowly added to the flask. The oil bath was heated to 125 ° C. for an additional 75 minutes, collecting the distillate. A total of 49.4 g of distillate was collected. The Dean-Stark trap was removed from the flask. The oil bath was kept at 125 ° C for an additional 95 minutes, the flask was removed from the oil bath and heating was discontinued. The flask was returned to the oil bath at 125 ° C for an additional 60 minutes. The flask was removed from the oil bath and 35 g of PGMEA was added to the flask to help facilitate cooling. The weight average molecular weight of the resulting silsesquioxane polymer was determined by GPC to be approximately 4255 g / mol. The targeted weight average molecular weight was 5000 g / mol. The flask was returned to the oil bath at 125 ° C. for an additional 61 minutes and then removed from the oil bath to determine its molecular weight. The weight average molecular weight was determined by GPC to be 4625 g / mol. The flask was returned to the oil bath at 125 ° C. for an additional 61 minutes and then removed from the oil bath to determine its molecular weight. The weight average molecular weight was determined by GPC to be 5015 g / mol. The concentration of the obtained silsesquioxane polymer solution was 22.71 wt%.
0127Prepolymer B Mix vinyltrimethoxysilane (13.6g), phenyltrimethoxysilane (3.4g), methyltrimethoxysilane (6.1g), glycidoxypropyltrimethoxysilane (10.8g) and PGMEA (80g) in a glass syringe. added. A 250 mL three-necked round bottom flask was charged with 3N acetic acid (9.2 g). The inside of the flask was mixed with an overhead stirrer. The silane / solvent blend was added to the flask at room temperature using a syringe pump and the total addition time was 70 minutes. After the addition of silane, the Dean-Stark trap and nitrogen line were connected to the flask. The flask was placed in an oil bath heated to 100 ° C. After collecting the distillate in the Dean-Stark trap for 43 minutes, PGMEA (40 g) was slowly added to the flask. The oil bath was heated to 125 ° C. for an additional 68 minutes, collecting the distillate. A total of 12.3 g of distillate was collected. The flask was removed from the heat and the Dean-Stark trap was removed. The weight average molecular weight was determined by GPC to be 645 g / mol. The flask was returned to the oil bath at 125 ° C. and after 120 minutes the sample was taken from the flask and the weight average molecular weight was determined by GPC to be about 1130 g / mol. Heating was continued for an additional 300 minutes. The flask was removed from the oil bath. The weight average molecular weight was determined by GPC to be 2050 g / mol. The flask was returned to the oil bath for 420 minutes, after which the weight average molecular weight was determined by GPC to be 3460 g / mol. The flask was returned to the oil bath for 420 minutes, after which the weight average molecular weight was determined by GPC to be 5480 g / mol. The concentration of the obtained silsesquioxane polymer solution was 14.03 wt% based on the weight of the solution.
0128Prepolymer C A temperature probe, a constant RPM overhead stirrer with a 2-inch Teflon® paddle, and a syringe pump addition adapter were attached to a three-necked 250 mL flask. Distilled silane monomer phenyltrimethoxysilane (7.03 g, 35.4 mmol), methyltrimethoxysilane (38.12 g, 279.8 mmol), and tetraethyl orthosilicate (16.42 g, 78.8 mmol) are weighed into a plastic bottle and placed in a reaction flask. Transferred and diluted with 65.5 mL of PGMEA. Dilute hydrochloric acid (0.1N, 3.95 mL, 3.95 mmol) with HPLC grade water (19.49 mL, 1082 mmol), mix in a graduated cylinder, then sprinkle 30 minutes into the silane solution with a syringe pump at ambient room temperature. And added drops. Immediately after completing the acid / aqueous solution addition step, the syringe pump addition adapter was replaced with a short-path distillation head equipped with a nitrogen line, after which the solution was heated in an oil bath with a set point of 110 ° C. After 15 minutes, the bath temperature setting point was lowered to 100 ° C. Reaction aliquots (0.2 mL) were frequently removed, diluted in THF (1.0 mL) and analyzed by GPC. The polymer solution reached a molecular weight close to the target (5000 g / mol) after heating for 75 minutes. The solution was diluted with additional PGMEA (46.8 mL, 342 mmol) to a 21.9 wt% solid relative to the total weight of the solution and cooled to room temperature. The solution was stirred on an excess equivalent of DOWEX MARATHON MR-3 mixed ion exchange resin manufactured by Dow Chemical Co. and filtered through a "0.2 μm" PTFE syringe filter. Molecular weight was measured by GPC: Mw 4079 g / mol; Mn 1798 g / mol; MWD 2.27.
0129Prepolymer D A temperature probe, a constant RPM overhead stirrer with a 2-inch Teflon® paddle, and a syringe pump addition adapter were attached to a three-necked 250 mL flask. Distilled silane monomer phenyltrimethoxysilane (7.08 g, 35.7 mmol), methyltrimethoxysilane (32.96 g, 242.0 mmol), and tetraethyl orthosilicate (24.79 g, 119.0 mmol) are weighed into a plastic bottle and placed in a reaction flask. It was transferred and diluted with 65.3 mL of PGMEA. Dilute hydrochloric acid (0.1N, 0.40 mL, 0.04 mmol) with HPLC grade water (23.2 mL, 1287 mmol), mix in a graduated cylinder, then sprinkle 30 minutes on the silane solution with a syringe pump at ambient room temperature. And added drops. Immediately after completing the acid / aqueous solution addition step, the syringe pump addition adapter was replaced with a short-path distillation head equipped with a nitrogen line. The materials were mixed for 60 minutes at ambient temperature, followed by an acid addition time of 30 minutes, after which the solution was heated in an oil bath with a set point of 100 ° C. After 5 hours, the bath temperature setting point was raised to 120 ° C. Reaction aliquots (0.2 mL) were frequently removed, diluted in THF (1.0 mL) and analyzed by GPC. The polymer solution reached a molecular weight close to the target (5000 g / mol) after heating for 6 hours. The solution was diluted with additional PGMEA (45.5 mL) to a 22.4 wt% solid and cooled to room temperature. The polymer solution was stirred on an excess equivalent of DOWEX MARATHON MR-3 mixed ion exchange resin. The solution was filtered through a "0.2 μm" PTFE syringe filter and stored in a freezer at approximately 15 wt% solid. Molecular weight was measured by GPC: Mw 7782 g / mol; Mn 2294 g / mol; MWD 3.39.
0130Prepolymer E A 250 mL three-necked round bottom flask was placed in a 20 ° C water bath. The flask was fitted with a stirrer connected to an air motor, a condenser with a water jacket, a thermocouple connected to a temperature controller, and an additive funnel. Acidified water (21.6 g, 1.2 mol, 3N acetic acid) was added to the flask. Vinyl trimethoxysilane (53.3 g, 0.360 mol) and phenyl trimethoxysilane (7.94 g, 0.040 mol) were premixed and added to the addition funnel. Silane was added to the reactor over 45 minutes. After the addition was complete, the water bath was removed and the heating mantle was placed under the flask. The addition funnel was removed and a Dean-Stark trap and nitrogen sweep line were connected. The solution was slowly heated in an oil bath set at 100 ° C. While heating, the distillate was collected in a trap. When the reaction reached 100 ° C, 100 g of PGMEA was added. The oil bath was slowly heated to 125 ° C, collecting additional distillate. The trap was removed when the bath temperature reached 125 ° C. After 3 hours, heating was stopped, 75 g of PGMEA was added and the solution was mixed until cooled to room temperature.
0131Prepolymer 6' A temperature probe, a constant RPM overhead stirrer with a 2-inch Teflon® paddle, and a syringe pump addition adapter were attached to a three-necked 250 mL flask. Distilled silane monomer phenyltrimethoxysilane (7.91 g, 39.9 mmol), methyltrimethoxysilane (18.10 g, 132.9 mmol), vinyltrimethoxysilane (36.74 g, 247.9 mmol), and tetraethyl orthosilicate (4.61 g, 22.1 mmol). ) Was weighed in a plastic bottle, transferred to a reaction flask, and diluted with PGMEA 81.65 mL. Glacial acetic acid (5.5 mL, 94 mmol) is diluted with HPLC grade water (21.9 mL, 1215 mmol), mixed in a graduated cylinder, and then added dropwise to the silane solution by syringe pump at ambient room temperature over 60 minutes. did. Immediately after completing the acid / aqueous solution addition step, the syringe pump addition adapter was replaced with a short-path distillation head equipped with a nitrogen line. The materials were mixed for 60 minutes at ambient temperature, followed by an acid addition time of 60 minutes, after which the solution was heated in an oil bath with a set point of 100 ° C. Reaction aliquots (0.2 mL) were frequently removed, diluted in THF (1.0 mL) and analyzed by GPC. The polymer solution reached a molecular weight close to the target (5000 g / mol) after heating for 9.5 hours. The solution was diluted with additional PGMEA (58.3 mL) to a 21.0 wt% solid and cooled to room temperature. The resin solution was filtered through a "0.2 μm" PTFE syringe filter and the polymer solution was stored in a freezer at approximately 20 wt% solid. Molecular weight was measured by GPC: Mw 4527 g / mol; Mn 1793 g / mol; MWD 2.52.
0132Prepolymer 7' A temperature probe, a constant RPM overhead stirrer with a 2-inch Teflon® paddle, and a syringe pump addition adapter were attached to a three-necked 500 mL flask. Distilled silane monomer phenyltrimethoxysilane (11.65 g, 58.7 mmol), methyltrimethoxysilane (44.42 g, 326.0 mmol), vinyltrimethoxysilane (34.85 g, 234.7 mmol) and tetraethyl orthosilicate (6.79 g, 32.6 mmol) Was weighed in a plastic bottle, transferred to a reaction flask, and diluted with 116.7 mL of PGMEA. Glacial acetic acid (8.10 mL, 138 mmol) is diluted with HPLC grade water (32.3 mL, 1792 mmol), mixed in a graduated cylinder and then added dropwise to the silane solution by syringe pump at ambient room temperature over 60 minutes. did. Immediately after completing the acid / aqueous solution addition step, the syringe pump addition adapter was replaced with a short-path distillation head equipped with a nitrogen line. The materials were mixed for 60 minutes at ambient temperature, followed by an acid addition time of 60 minutes, after which the solution was heated in an oil bath with a set point of 100 ° C. Reaction aliquots (0.2 mL) were frequently removed, diluted in THF (1.0 mL) and analyzed by GPC. The polymer solution reached a molecular weight close to the target (5000 g / mol) after heating for 10.5 hours. The solution was diluted with additional PGMEA (83.3 mL) to a 22.3 wt% solid and cooled to room temperature. The resin solution was filtered through a "0.2 μm" PTFE syringe filter and the polymer solution was stored in a freezer at approximately 20 wt% solid. Molecular weight was measured by GPC: Mw 4384 g / mol; Mn 1722 g / mol; MWD 2.55.
0133Prepolymer 8' A 250 mL three-necked round-bottomed flask equipped with a magnetic stirrer and a short-path distillation apparatus was loaded with phenyltrimethoxysilane (4.86 g), methyltrimethoxysilane (22.24 g), and vinyltrimethoxysilane (20.57 g). I entered. A solution of glacial acetic acid (5.15 g) and water (23.53 g) was added to the flask and stirring was started. Tetraethyl orthosilicate (17.01 g) was then added and the mixture was stirred for 60 minutes at room temperature. Initially, the phase-separated reaction mixture was homogenized as the hydrolysis progressed, a clear solution was obtained, and exotherm was observed. PGMEA (70 g) was added and the flask was placed in a temperature controlled oil bath. The oil bath was heated to 100 ° C for 1 hour, then to 110 ° C for 1 hour and then to 120 ° C. When the temperature of the reaction mixture reached 100 ° C, the heating bath was removed and the polymer solution was cooled. A second aliquot of PGMEA was added to prepare the polymer solution to a 20 wt% solid. The solid content of the polymer solution was determined by heating a small sample of the polymer solution in an oven at 145 ° C for 1 hour. The molecular weight of the polymer was determined by GPC: Mw 2071; Mn 1268; MWD 1.63.
0134Prepolymer 9' A 250 mL three-necked round-bottomed flask equipped with a magnetic stirrer and a short-path distillation apparatus was loaded with phenyltrimethoxysilane (4.84 g), methyltrimethoxysilane (22.24 g), and vinyltrimethoxysilane (20.58 g). I entered. A solution prepared from "0.1N HCl (0.41 g)" and water (23.22 g) was added to the flask and stirring was started. Tetraethyl orthosilicate (17.02 g) was then added and the mixture was stirred for 60 minutes at room temperature. Initially, the phase-separated reaction mixture was homogenized as the hydrolysis progressed, a clear solution was obtained, and exotherm was observed. PGMEA (50 g) was added and the flask was placed in a temperature controlled oil bath. The oil bath was heated to 100 ° C for 1 hour, then to 110 ° C for 1 hour and then to 120 ° C. When the temperature of the reaction mixture reached 100 ° C, the heating bath was removed and the polymer solution was cooled. A second aliquot of PGMEA was added to prepare the polymer solution to a 20 wt% solid. Residual acid, The Dow Chemical It was removed by passing a polymer solution through an ion exchange column packed with AMBERLITE IRN 150 mixed bed ion exchange resin manufactured by Company. The solid content of the polymer solution was determined by heating a small sample of the polymer solution in an oven at 145 ° C for 1 hour. The molecular weight of the polymer was determined by GPC: Mw 2925; Mn 1540; MWD 1.9.
0135Formation of second composition All second compositions, with the exception of second composition 9', were formed according to the general procedures described herein unless otherwise noted.
0136The specified prepolymer (37.5 g), BTEAC (0.37 g), and PGMEA (263 g) are added to the plastic bottle, mixed well and filtered through a 0.2 μm PVDF filter to form the respective second composition. I let you.
0137For the second composition 9', prepolymer 8 (37.5 g) and PGMEA (263 g) were added to the plastic bottle, mixed well, filtered through a "0.2 μm" PVDF filter and the second composition 9 'Formed. Table 3 summarizes all of the second compositions used in this study.
0138<tables num="3"><img id="000021" he="110" wi="153" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>
0139ArF Positive Tone Development (PTD) photoresist formation Suitable positive tone developed photoresists are formed from the following mixture: propylene glycol methyl ether acetate 28.60 g, cyclohexanone 19.30 g, hydroxybutyric acid methyl ester 48.25 g, molar ratios 20/20/30/20/10 respectively Isopropyl methacrylate-adamantyl, methylcyclopentyl methacrylate, methacrylic acid (3aR, 4s, 5R, 7S, 7aR) -3-oxooctahydro-4,7-epoxy-isobenzofuran-5-yl, with a weight average molecular weight of 9,000. Copolymer of hydroxyadamantyl methacrylate 3.02g, 1,1-difluoro-2-(((1r, 3s, 5R, 7S) -3-hydroxyadamantan-1-yl) methoxy) -2-oxoethanesulfonic acid (4- 0.46 g of (tert-butyl) phenyl) diphenylsulfonium, 0.04 g of tert-butyl (1,3-dihydroxy-2- (hydroxymethyl) -propan-2-yl) carbamate, and 0.01 g of PolyFox 656 fluorinated surface leveling agent. ..
0140ArF Negative Tone Development (NTD) photoresist formation Suitable negative tone developing photoresists are formed from the following mixtures: propylene glycol methyl ether acetate 28.95 g, cyclohexanone 19.30 g, hydroxybutyric acid methyl ester 48.25 g, weight average with molar ratios of 25/25/40/10 respectively. Methacrylic acid (2,2-dimethyl-1,3-dioxolan-4-yl) methyl and 5-(2,2-dimethyl-1,3-dioxolan-4-yl) -2,2 methacrylic acid having a molecular weight of 22,000 -Dimethyltetrahydroflo [2,3-d] [1,3] dioxol-6-yl, methyladamantyl methacrylate / 5-oxo-4-oxa-tricyclonona-2-yloxycarbonylmethyl methacrylate, hydroxyadamantyl acrylate Copolymer 2.89 g, 1,1,2,2-tetrafluoro-4-((4- (13-methyl-3,7,12-trioxohexadecahydro-1H-cyclopenta [a] phenanthrene-17-yl) ) Pentanoyl) Oxy) Triphenylsulfonium butane-1-sulfonate 0.49 g, n-butyl methacrylate polymer with a weight average molecular weight of 10,000 0.07 g, dodecyldiethanolamine 0.05, and PolyFox 656 fluoride surface leveling agent 0.01 g.
0141Formation of single layer coating An unprimed "200 mm" diameter silicon wafer from WaferNet Inc. was used as the substrate in a clean room environment (approximately 72 ° F, approximately 50% RH, class 100). The second composition was manually applied onto a Si wafer and spin coated on a Tokyo Electron (TEL) ACT-8 coated track to a nominal film thickness of 35 nm (as measured by a THERMA-WAVE spectroscopic ellipsometer). The coated wafer was baked at 240 ° C. for 60 seconds. Single layer coatings are summarized in Tables 4A, 4B and 4C.
0142<tables num="4"><img id="000022" he="77" wi="153" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>
0143Test method for single layer coating Measurement of optical properties (n, k at 193 nm) and film thickness Optical properties and film thickness were measured using a WOOLAM VUV-VASE VU-302 ellipsometer (Woolam, NE). The film was coated on a "200 mm" diameter bare silicon wafer as described above in the Single Layer Coating section. Polarization data was collected at three angles over the wavelength range from 170 nm to 900 nm. The data are automatically generated and the film thickness and index of index at 193 nm (n, k) (where n is the real part of the complex index and k is the imaginary part of the complex index. )was gotten.
0144Table 5 summarizes the refractive indexes n and k at 193 nm of Examples of the present invention and Comparative Examples. Minimization of reflection depends on the optical constants and thickness of the antireflection layer. For desirable thicknesses between 20 nm and 50 nm, computer simulations using PROLITH software V10.0 (KLA-Tencor Corporation) show that at 193 nm n is greater than or equal to 1.67 to reduce reflections to less than 0.5%. k indicates that it is from 0.15 to 0.3. As shown in Table 5, all examples of the present invention have n and k values within the required range, and each of the two comparative examples has a lower n value than required. Therefore, the examples of the present invention can provide good performance in controlling reflections and are therefore good antireflection layers, while the comparative examples are inferior in this respect.
0145<tables num="5"><img id="000023" he="84" wi="153" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>
0146Measurement of water contact angle Single-layer coatings were analyzed within 1 hour of coating, as discussed above. DATAPHYSICS Instruments GmbH, OCA20 type goniometer was used for all contact angle measurements. Deionized water was used as the test solution. One microliter droplet was used to determine each contact angle. After the droplets were applied on the surface of the monolayer coating, the droplet motion was recorded for at least 10 seconds for each measurement using a goniometer camera at a minimum speed of 3 frames per second. When the goniometer needle moved completely out of the field of view and no droplet motion was present, the first droplet image was used to determine the contact angle. Contact angles were evaluated using a circular model in OCA software. At least 3 separate measurements were made across the monolayer coating (3 drops per monolayer coating). The standard deviation typical for contact angle measurements is about 0.2 degrees.
0147Table 6 summarizes the water contact angle results of Examples and Comparative Examples of the present invention. Film quality is important for obtaining good patterns during the photolithography process. The layer of the invention is likely to be used in a multi-layer scheme with another layer coated on top of the layer of the invention. If the surface energy of the layer of the invention is too low, as indicated by the high water contact angle, defects such as dewet that occur when the film does not completely cover the coated area will be present in the layer of the invention. May appear in the membrane layer above. In order to minimize the surface defects of the adjacent layer, the water contact angle of the layer of the present invention is preferably less than 87 °. As shown in Table 6, Examples of the present invention have a water contact angle less than the contact angle of Comparative Example, and Examples 1 to 8 of the present invention have a contact angle of less than 87 °. By comparison, Comparative Examples C and D have water contact angles of 90 ° and 93 °, respectively.
0148<tables num="6"><img id="000024" he="90" wi="153" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>
0149Formation of two-layer coating The membrane was coated as described in the section on forming a single layer coating. ArF PTD photoresist is then applied to the spin-coated wafer and the coated wafer is soft-baked at 100 ° C for 60 seconds to 100 nm (as measured by a Thermo-Wave spectroscopic ellipsometer). The photoresist film thickness of was obtained. A two-layer summary is provided in Table 7.
0150<tables num="7"><img id="000025" he="83" wi="153" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>
0151Evaluation of adhesion of two-layer coating After the two-layer coating was formed, an adhesion test was performed. Adhesion tests used tape pull with reference to ASTM D3359. First, a piece of Scotch tape (3M, MN) was pressed firmly onto the ArF PTD photoresist coating. The length of the glued compartment was 1 inch and the remaining free connection compartments were at least 1 inch. The free section of the tape was grasped with two fingers and quickly pulled back at an angle of approximately 270 ° to the coated surface. After the tape was pulled, the remaining coating was visually examined and the area of the coating transferred to the tape was estimated as a percentage of the surface area of the tape adhered to the coating. "0% peeling" indicated good adhesion, while "100% peeling" indicated poor adhesion. The test was repeated at least 5 times and the average area of the coated coating was reported as shown in Table 8.
0152The three-layer coating for pattern lithography needs to have good interlayer adhesion. If the bond is weak, delamination may occur during lithography or pattern collapse occurs when the bond is less than different types of forces such as residual force, thermal stress, solvent swelling stress, and capillary force. Sometimes. Table 8 shows that all examples of the present invention have good adhesion, while comparative examples have inadequate interlayer adhesion.
0153<tables num="8"><img id="000026" he="75" wi="153" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>
0154Formation of three-layer coating The layers of the present invention were used in a three-layer scheme and the lithography performance was investigated. The general structure of the three layers is shown in Figure 1.
0155Lower layer formation An organic poly (methacrylate) -based undercoat composition was applied by spin coating to a "300 mm" diameter silicon wafer available from WaferNet, Inc. and the coated wafer was baked at 240 ° C for 60 seconds. A film thickness of 135 nm was obtained. Suitable underlayer coating compositions include AR26N available from Dow Chemical Company.
0156Formation of the layer of the present invention on the lower layer The coating composition of the present invention shown in Table 9 was applied to the wafer coated in the lower layer from the previous step by spin coating. Each coating was baked at 240 ° C. for 60 seconds to give the film thickness of the present invention at 35 nm.
0157Formation of three layers ArF photoresist (both PTD and NTD as described above) is applied to the coated wafer from the previous step by spin coating and the coated wafer is applied at 100 ° C for 60 seconds. Soft baking gave a photoresist film thickness of 100 nm. A topcoat can be applied to the PTD photoresist coating to provide the desired leaching control for the "193 nm" immersion graphic process. Suitable topcoats include OC2000 from Dow Chemical Company.
0158<tables num="9"><img id="000027" he="19" wi="153" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>
0159Graphic pattern formation Graphic processing The formed three-layer coating was treated according to the following steps: 1) Exposure: The coated photoresist layer was exposed to patterned 193 nm irradiation using ASML 1900i; 2) Post-exposure bake: 120 ° C for 60 seconds; 3) Develop: Latent image with 0.26N aqueous alkaline developer to provide positive photoresist relief image, or suitable organic solvent to provide negative photoresist relief image (OSD-1000 from Dow Chemical Company) Developed with Organic Solvent Developer etc.).
0160Evaluation of graphic performance of three-layer coating FIG. 2 depicts a schematic cross section of two photoresist lines. A desirable photoresist line cross section is shown in FIG. 2a. The cross section shows a square profile. The undesired cross-sectional profile is shown in Figure 2b. Undesirable cross sections indicate an increase in CD (marginal dimension) at the feature bottom. This profile defect is commonly referred to as footing or scum.
0161Another aspect of photoresist performance is the "pattern collapse margin". It is desirable to be able to obtain very small line-space patterns while preventing or reducing such small line-space pattern "fall over" or fall. Hardmask compositions that do not provide sufficient adhesion to the photoresist can result in pattern collapse, as shown in the top-down SEM image in FIG. Figure 4 illustrates the quantitative definition of the pattern collapse margin. The numbers in this figure are the groove widths in the "140 nm pitch pattern". The higher the pattern collapse margin, the narrower the width of the standing line, and therefore the better the lithography performance with respect to the smallest dimensions that can be formed.
0162After the lithography process, it is highly desirable to obtain a photoresist pattern with a high pattern collapse margin without scum. Table 10 compares the profile cleanliness (lack of scum) of the examples of the present invention and the comparative examples. FIG. 5 shows that Example 16 of the present invention has a square profile without scum, while scum was observed in the profile of Comparative Example G as shown in FIG. Table 11 compares the pattern collapse margins of the examples of the present invention and the comparative examples. As shown in this table, the examples of the present invention had a good pattern collapse margin, while the comparative examples had a complete pattern collapse.
0163<tables num="10"><img id="000028" he="26" wi="153" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>
0164<tables num="11"><img id="000029" he="41" wi="153" file="JP6006594B2_D0001.tif" img-format="tif" img-content="drawing" /></tables>
38 sheets
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Numbers
- Publication
- 6006594
- Application
- 207144
Titles2
- Japanese
- フォトリソグラフィのための組成物および反射防止コーティング
- English
- Compositions and anti-reflective coatings for photolithography
Classification
- CPC, 8
- G03F7/0752
- G03F7/091
- Y10T428/31663
- B05D1/002
- G02B1/111
- G03F7/0042
- G03F7/0043
- G03F7/0045
- IPC, 3
- C08G77 20
- G03F7 11
- H01L21 027
