TWI358431B - - Google Patents

Description

1358431

[Technical Field] The present invention relates to a cerium oxide-based coating for forming a cerium oxide-based coating. More specifically, it relates to a composition for forming a bismuth-based film which can be formed into a film at a low level and a ruthenium dioxide film. [Prior Art] A composition for forming a cerium oxide-based film is used to form a dioxo film, and is mainly used for gradation of a semiconductor wiring or the like, or a trench filling. Since it is a coating liquid, even if the pattern concave on the wafer can be easily filled, it can be flattened with good reproducibility. Further, the cerium oxide-based coating film is particularly suitable for use as an insulating film. Such a bismuth-based bismuth-based coating film can be usually formed by coating a composition for forming a cerium oxide-based composition on a substrate and then baking it at a temperature of 2.8 to 300 ° C and baking at a temperature of 305 ° C or higher. (Patent Document 1) [Patent Document 1] Japanese Laid-Open Patent Publication No. Hei. No. 2005- 1 71 067. SUMMARY OF THE INVENTION [Problems to be Solved by the Invention] As described above, it is necessary to perform at a high temperature of 350 ° C or higher. The calcination results in a decrease in productivity, and the calcination at a high temperature causes decomposition of the bonded organic groups, which is not a good condition for exhibiting the use of the cerium oxide-based coating. Wiring is also a layer of film and processing and 矽 characteristics 5 1358431

In view of the above problems, an object of the present invention is to provide a composition for cerium oxide which can form a cerium oxide-based coating film by heating. [Means for Solving the Problems] In order to solve the above problems, the inventors of the present invention have focused on the addition of an additive for forming a composition for forming a film, and have repeatedly studied the use of a compound which generates an acid or a base by thermal action, thereby completing the present invention. . More specifically, the present invention provides a cerium oxide-based composition comprising a cerium oxide polymer (A) and a compound of a hot or alkali compound (B). Furthermore, the second invention of the present invention is a cerium oxide-based coating obtained by using the above-described composition for oxidation. [Effects of the Invention] The composition for forming a cerium oxide-based film of the present invention acts as a compound which generates an acid or a base. Thereby, the cerium oxide-based coating can be easily formed without being able to. [Embodiment] Hereinafter, embodiments of the present invention will be described. <<Composition for forming a oxidized particle-forming film>> The composition for forming a cerium oxide-based film of the present invention, the alkyl polymer (A), and an acid or a base are generated by the action of heat. The ruthenium dioxide is formed by a film at a low temperature. As a result, I will solve the above items. The film is formed to form an acid lanthanide film containing a temperate b compound (B) by a temperature of 350 ° C. 6 1358431

&lt;Hexane-Containing Polymer (A)&gt; The siloxane polymer (A) (hereinafter, also referred to as "1") of the present invention is not particularly limited, and is a polymer having a Si-0-Si bond. Among the siloxane polymers (A), it is preferred to use alkoxy hydrazine to decompose the condensate. As the alkoxydecane, the alkoxydecane can be used. The alkoxydecane may, for example, be a compound represented by the following (a). R1 „-Si(OR2)4-n (4) (wherein R1 represents hydrogen, an alkyl group or an aryl group having 1 to 20 carbon atoms, an organic group of R2, and an integer of η of 0 to 2; Here, examples of the monovalent organic group include an alkyl group, an allyl group, and a glycidyl group. Among these, the carbon number of the group and the arylalkyl group is 1 to 5 Preferably, for example, a mercapto group, an ethyl group, a butyl group, etc. may be mentioned. Further, the alkyl group may be linear or branched or substituted by fluorine. The aryl group is a carbon number of 6 to 20 For example, a specific example of the compound represented by the above formula (a) (al) η = 0 may be tetramethoxy decane, tetraethane or tetrapropyl. Oxydecane, tetrabutoxydecane, etc., (a2) When n = 1, monomethyltrimethoxydecyltrimethoxydecane, monomethyltripropoxydecane, monoethyl Monoalkyl (A) such as trioxane, monoethyltriethoxydecane, monoethyltripropoxydecyltridecyloxydecane, monopropyltriethoxydecane, etc. The above formula is preferably a valent group or a aryl group. A group, a propyl group, and a hydrogen group. Oxyquinone, monomethyloxy, propylene oxide 7 1358431 alkyl alkoxide, methane trimethylphenyl phenoxy oxide such as oxygen, trialkylmethane phenyl isodecyloxy Tribasic methyl dioxy- decane dimercapto ethoxy dimethyl, dialkyl fluorenyl dioxy propylene has a di-negative enthalpy, </ br>, alkane 2 矽 II η η 3) Oxygen (a ethanediyl decane, diethyl diethoxy decane, diethyl dipropoxy decane, dipropyl decyloxy decane, dipropyl diethoxy decane, dipropyl dipropoxy a dialkyl dialkoxy decane such as a dialkyl dialkoxy decane, a diphenyl decyloxy decane or a diphenyl diethoxy decane such as a decane or the like. The composition for forming a film, the weight average molecular weight of the siloxane polymer (A) is preferably 200 or more and 50,000 or less, more preferably 1,000 or more and 3,000 or less. In this range, the cerium oxide-based film can be formed. The coating property of the composition. The hydrolysis and condensation of the alkoxydecane can be achieved by alkoxylation of the polymerizable monomer. The decyl alkane is obtained by a reaction in the presence of an acid catalyst or a base catalyst in an organic solvent. The alkoxy decane of the polymerizable monomer may be used singly or in combination of two or more kinds. Further, trimethyl methoxy decane, trimethyl ethoxy decane, trimethyl propyl oxy fluorene, triethyl methoxy cesium, triethyl ethoxy decane may be added during hydrolysis. a trialkylalkoxydecane such as triethylpropoxydecane, tripropyldecyloxydecane or tripropylethoxydecane; trisuccinyloxydecane, triphenylethoxydecane, etc. The degree of hydrolysis of the alkoxydecane which is a prerequisite for the condensation can be adjusted by the amount of water added. Usually, the total molar amount of the alkoxy calcination shown in the above chemical formula (a) is such that the water is added in an amount of 8 1358431 1.0 to 10.0 times the molar amount, and the ratio is 1.5-8.0 times the molar amount. Better. By adding the amount of water to 1.0 times or more, the degree of hydrolysis can be sufficiently increased, and the film can be formed favorably. On the other hand, gelation can be prevented by 1 〇. 倍 mM or less, and storage stability can be improved.

Further, the condensation of the oxy-oxyl compound represented by the chemical formula (a) is preferably an acid catalyst, and the acid catalyst to be used is not particularly limited, and any of the organic acids and inorganic acids which have been conventionally used can be used. . The organic acid may, for example, be an organic carboxylic acid such as acetic acid, propionic acid or butyric acid; and the inorganic acid may, for example, be hydrochloric acid, nitric acid, sulfuric acid or phosphoric acid. The acid catalyst may be directly added to the mixture of alkoxy decane and water; or it may be added to the alkoxy decane as an acidic aqueous solution together with water.

The hydrolysis reaction system is usually completed in about 5 to 100 hours. Further, it is also possible to add an acid catalyst aqueous solution to an organic solvent containing one or more kinds of alkoxysilanes represented by the chemical formula (a) at room temperature to a heating temperature of not more than 80 °C. The reaction is completed in a shorter reaction time. The hydrolyzed alkoxysilane is then subjected to a condensation reaction, and as a result, a network structure of Si-0-Si is formed. <Compound (B) which generates an acid or a base by thermal action&gt; A compound which produces an acid or a base by heat (hereinafter also referred to as "(B) component)", as long as it can generate an acid or a base by heating, It can be used without particular limitation. Further, a compound which generates an acid or a base is preferably a compound which generates an acid or a base at 100 ° C or more and 300 ° C or less. The cerium oxide-based film forming composition can form a cerium oxide-based coating film 1358431 by containing the component (B) described above and baking it at a high temperature of, for example, 3 50 ° C or higher. Thereby, heating (for example, drying and baking) after coating the composition for forming a ceria-based coating film can be simplified. Further, by containing the component (B), the resistance to fluoro acid or the like can be improved.

Such a substance may, for example, be a thermal acid generator or a thermal base generator. The thermal acid generator is not particularly limited, and 2,4,4,6-tetrabromocyclodione, benzoin tosyl ate, and 2-nitrohexyl phthalate can be used. 2-nitrobenzyl tosylate), alkyl esters other than organic sulfonic acids, and the like. There are sputum salts such as salt, moth salt, benzo thiazonium salt, salt, and strontium salt. Among them, specific examples of the iodonium salt, the phosphonium salt, and the benzothiazolium salt are particularly preferred, and the benzothiazolium salt is exemplified by, for example, 4-ethyloxyphenyl dimethyl 4-ace.toxy phenyl dimethyl sulfonium hexafluoro arsenate, benzyl-4-hydroxyphenylmethyl hexafluoroantimonate, 4-ethoxycarbonylphenylbenzyl sulfonate Fluoride, dibenzyl-4-hydroxyphenyl hexafluoroantimonate, 4-ethoxycarbonylphenylbenzyl hexafluoroantimonate, 3-benzyl benzothiazolium hexafluoroantimonate Salt and so on. Further, the thermal base generator is not particularly limited, and 1-methyl-1 -(4-biphenylylethylcarbamate, 1,1-dimethyl-2-cyanoethyl group can be used. Amino phthalate derivatives such as urethanes; urea derivatives such as urea or N,N-dimethyl-Ν'-methylurea; dihydrogens such as 1,4-dihydroanilinamide a pyridine derivative; a quaternary ammonium salt of an organic decane or an organoborane, a dicyanodiamine, etc. Further, there are ruthenium trichloroacetate, ruthenium trisacetate, potassium triacetate, Styrene sulfonate hydrazine, p-phenyl phenyl sulfonate hydrazine, 10 1358431 p-methylsulfonyl sulfonate hydrazide, phenyl propiolate, phenyl propiolate, phenyl propylic acid planer, P-Phenylphenylpropynoate, p-Phenyl-bis-phenylpropynoyl hydrazide, phenylsulfonate tetramethylammonium, phenylpropynoic acid tetramethylammonium, etc. The compound represented by the chemical formula (b1) and the following chemical formula (b-2) is particularly preferable. [Chemical Formula 2] N〇2

[Chemical Formula 3]

(b-2) Further, these compounds which generate an acid or a base may be used alone or in combination of two or more. The content of the component (B) is preferably 0.1% by mass or more and 20% by mass or less based on the mass of the SiO 2 equivalent of the component (A), and more preferably 0.5% by mass or more and 15% by mass of 1,538,441% or less. By setting the component (B) in the above range, the stability with time of the composition for forming a cerium oxide-based film can be improved. &lt;Other components&gt; (Surfactant) The composition for forming a cerium oxide-based film of the present invention is preferably formulated with a surfactant. The coating property and the spreadability to the substrate can be improved by the presence of the surfactant.

(solvent)

In order to improve the coating property and the uniformity of the film thickness, the composition for forming a cerium oxide-based film of the present invention preferably contains a solvent. The solvent can use an organic solvent which has been conventionally used. Specific examples include methanol, ethanol, propanol, butanol, 3-decyloxy-3-mercapto-1-butanol, 3-methoxy-1-butanol monohydric alcohol; An alkyl carboxylate of methoxy methoxypropionate or ethyl 3-ethoxypropionate; a polyol such as ethylene glycol, diethylene glycol or propylene glycol; such as ethylene glycol monodecyl ether, ethylene glycol Monoethyl ether, ethylene glycol monopropyl scale, ethylene glycol monobutyl mystery, propylene glycol monomethyl mystery, propylene glycol monoethyl mystery, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene a polyol derivative of an alcohol monodecyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate; a fatty acid such as acetic acid or propionic acid Acetone, mercaptoethyl ketone, 2-heptanone ketone, and the like. Among these, an alcohol-based or glycol-based solvent is preferably used. Further, these organic solvents may be used singly or in combination of two or more. The amount of the solvent is not particularly limited, and the concentration of the component (solid content) other than the solvent is preferably 5 to 100% by mass, more preferably 20 to 50% by mass. 12 1358431 By being within this range, coatability can be improved. (Others) Further, in the present invention, other resins, additives, and the like can be blended in a range that does not impair the effects of the present invention. <<Method for Forming Cerium Oxide Film>

In the method of forming a cerium oxide-based coating film, first, a composition for forming a cerium oxide-based coating film is applied onto a substrate. For the method of applying the composition for forming a cerium oxide-based film onto a substrate, for example, a spray coating method, a spin coating method, a roll coating method, or the like can be used, and a spin coating method can be usually used. Next, the composition for forming a cerium oxide-based film which has been applied onto the substrate is subjected to heat treatment. The means for heat treatment, temperature, time and the like are not particularly limited, and it is usually heated on a hot plate of about 80 to 300 ° C for about 1 to 6 minutes.

According to the composition for forming a cerium oxide-based film of the present invention, heating is carried out by heat treatment to generate an acid or test. Since the acid or base produced promotes hydrolysis, the alkoxy group becomes a hydroxyl group and forms an alcohol. Then, since two molecules of the alcohol are condensed to form a network structure of S i - 0 - S i , a fine cerium oxide-based film can be obtained by heat treatment. Further, the heat treatment is preferably three or more stages, and it is preferred to increase the temperature in stages. Specifically, in the atmosphere of an inert gas such as nitrogen or nitrogen, the first heat treatment is performed on a hot plate of about 60 to 150 ° C for about 30 seconds to about 2 minutes, and then it is about 100 to 220 ° C. On the hot plate, after the second heat treatment for about 30 seconds to 2 minutes, the third heat treatment is performed for about 30 seconds to 2 minutes on a hot plate at about 150 to 300 °C, 13 1358431. By performing the stepwise heating treatment of three or more stages, preferably about three to six stages, the cerium oxide-based coating film can be formed at a relatively low temperature. [Examples] Next, the present invention will be described in more detail based on examples, but the present invention is not limited to these examples. &lt;Example 1 &gt;

Spin-On Glass material (OCDT-12 l〇〇〇V (trade name)) containing a hydrolyzed product of trialkoxydecane as a main component:

The compound (b-1) was added to the solid content of the spin-on glass material in an amount of 5% by mass based on the solid content of the spin-on glass material. A composition for forming a cerium oxide-based film is produced. Using a coater (SS8261NUU: manufactured by Tokyo Ohka Kogyo Co., Ltd.), the composition for forming a cerium oxide-based film was coated on a 6-inch ruthenium wafer at a number of revolutions of 100 rpm. Connect #, on the hot plate at 8 〇. . Heating was carried out for 60 seconds, heating at 150 ° C for 60 seconds, and heating at 2 Torr for 6 seconds to form a cerium oxide-based coating. &lt;Example 2&gt; A spin-on glass material containing a hydrolyzed product containing tetradecyloxydecane/monomethyltrimethoxydecane=wi (mole ratio) (〇cd丁_7 7_WK80A (trade name) Manufactured by the Tokyo Chemical Industry Co., Ltd. (solid content concentration: 7 mass%), the compound (bl) is added to the solid content of the spin-on glass material at 7 mass% to produce cerium oxide. It is a composition for film formation. The composition of the cerium oxide-based film-forming film was applied onto a 6-inch ruthenium wafer at a number of revolutions of 1,000 rpm using an applicator (SS826inuu: 14 1358431, manufactured by Tokyo Ohka Kogyo Co., Ltd.). Subsequently, heating was carried out at 300 ° C for 60 seconds on a hot plate to form a cerium oxide-based flag. &lt;Comparative Example 1 &gt; A cerium oxide-based coating film was produced by the same method as in Example 1 using OCD T-12 1000V. &lt;Comparative Example 2&gt; After heating in Comparative Example 1', it was subjected to selective firing at 4 °C under a nitrogen atmosphere to form a oxidized coating film. <Comparative Example 3:&gt; A cerium oxide-based coating film was produced by the same method as in Example 2 using OCD T-7 7000WK80A. &lt;Comparative Example 4 &gt; After heating in Comparative Example 3', it was calcined at 400 ° C in a nitrogen atmosphere to form a oxidized hair-based coating film. <Evaluation of film formation property> The film formation property evaluation was carried out using FT-IR (FTIR-615 (trade name): manufactured by JASCO Corporation). In Example 1 and Comparative Examples 1 and 2, the evaluation was made by the ratio of the sharp area of the Si-Ο bond to the sharp area of the SiH bond. Example 2 and Comparative Examples 3 and 4 were evaluated by the ratio of the sharp area of the Si_〇 bond to the sharp area of the Κ bond. Further, in the FT-IR diagram, the spike system near 1050 cm indicates the Si-0 bond, the spike near 2250 cm.1 indicates the Si-H bond, and the spike near 1275 cm-i indicates the sic bond. The results are shown in Tables 1 and 2. Further, the FT-IR diagram of the first embodiment is 15 1358431. As shown in Fig. 1, the FT-IR diagram of the comparative example 1 is as shown in Fig. 2, and the FT-IR diagram of the embodiment 2 is as shown in Fig. 3. The FT-IR diagram of Comparative Example 3 is shown in FIG. 4,

[Table 1] Film thickness (A) Si-0/Si-H Example 1 4591 3.756 Comparative Example 1 4325 2.364 Comparative Example 2 4221 3.164 [Table 2] . Si-0/Si-C Example 2 37.645 Comparative Example 3 33.562 Comparative Example 4 37.209

According to Tables 1 and 2, when compared with Comparative Example 1 and Comparative Example 3 in which no additive (compound (b-Ι)) was added, Examples 1 and 2 in which additives were added were confirmed to be at 200 ° C or lower. By heating, a network structure of Si-0-Si can be formed. Further, when compared with Comparative Examples 2 and 4 which were fired at 400 ° C, the Si-0/Si-H ratio was high, and it was confirmed that the formed Si-0-Si network structure was compared with that of baking. , the system is equal to or above. Furthermore, the amount of film reduction of the time after the application of buffered hydrofluoric acid (BHF) to the above-mentioned ceria coating film was measured for the ceria coating film of the above-mentioned Example 2 and the comparative example 3, and the mass of 3 was confirmed. % concentration of B HF tolerance. The result is shown in Figure 5. As is clear from Fig. 5, when compared with Comparative Example 3, it was confirmed that the film of Example 13 of Example 1 was high in chemical resistance. BRIEF DESCRIPTION OF THE DRAWINGS Fig. 1 is a view showing the FT-IR of the first embodiment. Fig. 2 is a view showing the FT-IR of Comparative Example 1. Fig. 3 is a view showing the FT-IR of Example 2.

Fig. 4 is a view showing the FT-IR of Comparative Example 3. Fig. 5 is a graph showing the B H F pair of the cerium oxide-based coating films of Example 2 and Comparative Example 3. [Main component symbol description] None

17

Claims (1)

1358431 L lion. X. Patent application scope: 1. A composition for forming a cerium oxide-based film comprising a siloxane polymer (A) and a compound (B) which generates an acid or a base by heat, and the ruthenium The oxyalkylene polymer (A) is a hydrolyzed condensate of an alkoxy decane, and the acid or base-producing compound (B) is a compound which generates an acid or a base at 100 ° C or more and 300 ° C or less. • 2 1 曰 Amendment The content of the acid or base-forming compound (B) is from 0.1% by mass to 20% by mass based on the SiO2 conversion mass of the component (A). 2. The composition for forming a cerium oxide-based film according to the first aspect of the invention, wherein the acid or base-generating compound (B) is represented by the following chemical formula (b-1) or (b-2) Compound, (b- 1 ) (2) The composition of the cerium oxide-based film forming method according to the first aspect of the invention, wherein the alkoxy decane contains at least one selected from the group consisting of the following a compound represented by the formula (a), R1n-Si(OR2)4. (4) (wherein R1 represents hydrogen, an alkyl group or an aryl group having 1 to 20 carbon atoms, and R2 is a monovalent organic group; η is an integer from 0 to 2). 4. A cerium oxide-based coating film obtained by using the composition for forming a cerium oxide-based coating film according to the first aspect of the invention. 19