KR101243339B1 - Method for preparing polysilazane solution and polysilazane solution prepared by the same - Google Patents
Method for preparing polysilazane solution and polysilazane solution prepared by the same Download PDFInfo
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Abstract
The present invention relates to a method for preparing a polysilazane solution and a polysilazane solution prepared using the same, a mixed solution preparation step of preparing a mixed solution by mixing halosilane in a mixed solvent containing a basic solvent and an inert solvent, A reaction solution preparation step of preparing a reaction solution by reacting halosilane included in the mixed solution and ammonia added to the mixed solution, a reaction filtrate preparation step of preparing a reaction filtrate by removing salt from the reaction solution, and the A polysilazane solution preparation step of preparing a polysilazane solution by removing the basic solvent from the reaction filtrate, wherein the reaction filtrate production step, the polysilazane solution production step and any selected from the group consisting of It further comprises a further ammonia addition step of adding ammonia after one step.
The method for producing the polysilazane solution may reduce the volume shrinkage rate when converting to the silicon oxide film due to the low shrinkage rate when applied as a coating solution for semiconductor gapfill, thereby minimizing the occurrence of tensile stress and thus preventing bit line cracking and voiding. have.
Description
The present invention relates to a method for producing a polysilazane solution with improved shrinkage and to a polysilazane solution prepared thereby, by reducing the volume shrinkage rate when switching to a silicon oxide film due to the low shrinkage rate when applied as a coating solution for semiconductor gap fill The present invention relates to a method for preparing a polysilazane solution capable of minimizing the generation of tensile stress and suppressing cracking and voiding of bit lines, and a polysilazane solution prepared by using the same.
When manufacturing a semiconductor device or the like, various structures such as a transistor device, a word line, a bit line, a capacitor and a metal wiring are formed on a substrate such as a silicon wafer. These structures utilize an insulating film to electrically insulate between the devices with conductivity.
The process of forming the insulating layer may include a premetal dielectric (PMD) process for insulating between a transistor element and a bit line, a bit line and a capacitor, a capacitor, and a metal wire, an interlayer dielectric (ILD) process for insulating the metal wire, and a trench between transistors ( and a shallow trench isolation (STI) process for filling the trench.
In the manufacturing process of the semiconductor device, an oxide film by HDP CVD (High Density Plasma Chemical Vapor Deposition) is applied as a gapfill layer in the ILD process and the STI process.
As semiconductor devices become highly integrated and the pattern spacing narrows, the trenches continue to narrow. According to recent design rules, the trench width is required to be 60 nm or less. In this case, a problem occurs in a semiconductor device fabrication process that has not occurred previously. For example, in a semiconductor device fabrication process having a design rule of 60 nm or less, when a CVD method is used to form a silicon oxide film in a trench, Because of the poor gap fill capability, bridges and voids are formed in the oxide film.
In order to overcome this problem, a technique for forming a silicon oxide film using a spin coating capable of manufacturing a semiconductor device has recently been developed. The composition receiving the most attention as a composition for manufacturing a semiconductor device is a composition containing polysilazane, which is converted to a silica or a silica material when heated, the silica material formed in this way is excellent in insulating properties, such as electrical and It is widely used in the electronic field.
Another problem that may occur when the insulating film is formed using the polysilazane is that the polysilazane is converted to a silicon oxide film, the volume shrinkage occurs due to a high shrinkage rate, which causes tensile stress in either direction It happens. Due to the excessive tensile stress, a biting (BL) phenomenon in which the bit line BL is inclined occurs, and a void is generated between the bit line and the silicon oxide layer. These problems also cause a problem that a subsequent inter-contact bridge occurs to reduce the productivity of the semiconductor device.
The polysilazane for forming the silicon oxide film can be manufactured by various methods. The polysilazane thus prepared needs to form an insulating film having excellent application properties such as uniform coating and a dense and good surface shape.
An object of the present invention is a polysilazane that can suppress the occurrence of bit line cracking and voids by minimizing the occurrence of tensile stress by reducing the volume shrinkage rate when switching to the silicon oxide film due to the low shrinkage rate when applied as a coating solution for semiconductor gap fill. It is to provide a method for preparing a solution.
Still another object of the present invention is to provide a polysilazane solution prepared using the method for preparing the polysilazane solution.
Method for producing a polysilazane solution according to an embodiment of the present invention is a mixed solution manufacturing step of preparing a mixed solution by mixing a halosilane in a mixed solvent containing a basic solvent and an inert solvent, halosilane contained in the mixed solution A reaction solution preparation step of preparing a reaction solution by reacting ammonia added to the mixed solution, a reaction filtration step of preparing a reaction filtrate by removing salt from the reaction solution, and removing the basic solvent from the reaction filtrate. A polysilazane solution manufacturing step of preparing a polysilazane solution, wherein ammonia is added after any one step selected from the group consisting of the reaction filtrate preparation step, the polysilazane solution preparation step, and a combination thereof Ammonia additional injection step further comprises.
The ammonia added in the additional ammonia addition step may be added in a molar ratio of 1: 0.01 to 1: 0.5 (ammonia added in the reaction solution preparation step: added ammonia added) with respect to the ammonia added in the reaction solution preparation step. have.
After adding the ammonia in the addition step of the ammonia addition may be reacted at -20 to 100 ℃.
A polymerization step of polymerizing the reaction filtrate at 40 to 120 ° C. for 6 to 300 hours may be further included between the reaction filtrate preparation step and the polysilazane solution preparation step.
The inert solvent included in the mixed solvent may be any one selected from the group consisting of dibutyl ether, xylene, toluene, ethylbenzene, benzene, and combinations thereof.
The basic solvent included in the mixed solvent may be any one selected from the group consisting of pyridine, triazine, triethylamine, and combinations thereof.
The mixed solvent may include the basic solvent and the inert solvent in a volume ratio of 1: 0.05 to 1:20.
In the reaction solution preparation step, the ammonia may be added in a molar ratio (halosilane: ammonia) of 1: 2 to 1: 8 based on the halosilane.
Polysilazane solution according to another embodiment of the present invention may be prepared by the method for producing the polysilazane solution.
Hereinafter, the present invention will be described in more detail.
Unless stated otherwise in the specification, the halogen atom is any one selected from the group consisting of fluorine, chlorine, bromine and iodine.
Unless stated otherwise in the specification, all compounds or substituents may be substituted or unsubstituted. Herein, substituted Iran hydrogen is a halogen atom, a hydroxy group, a carboxy group, a cyano group, a nitro group, an amino group, a thio group, a methyl thio group, an alkoxy group, a nitrile group, an aldehyde group, an epoxy group, an ether group, an ester group, an ester group , Carbonyl group, acetal group, ketone group, alkyl group, cycloalkyl group, heterocycloalkyl group, allyl group, benzyl group, aryl group, heteroaryl group, derivatives thereof, and combinations thereof.
Unless stated otherwise in the specification, an alkyl group includes a primary alkyl group, a secondary alkyl group, and a tertiary alkyl group.
Method for producing a polysilazane solution according to an embodiment of the present invention includes a mixed solution preparation step, a reaction solution preparation step, a reaction filtrate production step, and a polysilazane solution production step, the reaction filtrate production step, the poly The addition of ammonia addition step of additionally adding ammonia after any one step selected from the group consisting of silazane solution production step and a combination thereof.
The mixed solution preparation step is a step of preparing a mixed solution by mixing halosilane in a mixed solvent containing a basic solvent and an inert solvent. In the case of using a basic solvent and an inert solvent as a mixed solvent used for synthesizing the polysilazane, stirring is easy, reaction efficiency can be increased, and further washing process can be reduced.
The basic solvent may be a solvent containing a basic amine group and a mixed solvent thereof, and specifically, trimethylamine, dimethylethylamine, diethylmethylamine, triethylamine, pyridine, picoline, dimethylaniline, trimethylphosphine, dimethyl It may be any one selected from the group consisting of ethyl phosphine, methyl diethyl phosphine, triethyl phosphine, trimethyl arsine, trimethyl stypine, trimethylamine, triethylamine, triazine and combinations thereof.
Preferably, the basic solvent may be any one selected from the group consisting of pyridine, triazine, triethylamine, and combinations thereof, and more preferably pyridine. When the pyridine is used as the basic solvent, there is a rapid rate of salt formation with halosilane and excellent properties in terms of economy.
The inert solvent may be a solvent that does not react with halosilane and ammonia, and a mixed solvent thereof, and may be any one selected from the group consisting of hydrocarbons, ethers, esters, and combinations thereof, and specifically, heptane and octane , Nonene, decane, undecane, dodecane, tetradecane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane, 2,2,4-trimethylpentane , 2,3,4-trimethylpentane, 2-methylhexane, 3-methylhexane, 2,2-dimethylhexane, 2,4-dimethylhexane, 2,5-dimethylhexane, 3,4-dimethylhexane, 2- Methylheptane, 4-methylheptane, methylcyclohexane, ethylcyclohexane, isopropylcyclohexane, 1,4-dimethylcyclohexane, 1,2,4-trimethylcyclohexane, cyclohexene, cyclopentane, decahydronaphthalene, p Menthane, dipentene (limonene), benzene, toluene, xylene, ethylbenzene, styrene, vinyltoluene, divinylbenzene, diethylbene , Trimethylbenzene, triethylbenzene, ethyl ether, isopropyl ether, ethyl butyl ether, butyl ether, dibutyl ether, ethylene glycol dimethyl ether, ethylene glycol diethyl ether, and combinations thereof. .
The inert solvent may be any one selected from the group consisting of dibutyl ether, xylene, toluene, ethylbenzene, benzene, and combinations thereof, and more preferably dibutyl ether.
In the case where the halosilane is added and reacted using only the existing basic solvent, an excess salt may be generated to cause a problem of stirring, and a salt formation reaction between the halosilane and the basic solvent may not be sufficiently performed. If the salt formation reaction is not sufficient, halosilanes may be vaporized to change the number of moles of the compound contributing to the reaction. However, when using the mixed solvent containing the inert solvent, it is possible to reduce the difficulty of stirring, to facilitate the reaction of the halosilane and the basic solvent, the amount of halosilane not reacting with the basic solvent Can be reduced.
The mixed solvent may be maintained at a temperature of -42 to -10 ℃, preferably at a temperature of -20 to -10 ℃. When the mixed solvent is maintained in the above temperature range, the heat of reaction generated when salts are formed between the halosilane and the basic solvent can be controlled to prevent vaporization of the halosilane due to the heat of reaction.
The mixed solvent may include the basic solvent and the inert solvent in a volume ratio of 1: 0.05 to 1:20, preferably in a volume ratio of 1: 0.2 to 1:10, and more preferably 1: 0.25. To 1: 4 by volume ratio.
When the volume ratio of the inert solvent to the basic solvent is less than 1: 0.05, gelation or molecular weight control may be difficult when applying a reaction temperature of 100 ° C. or higher, and when it exceeds 1:20, the reaction time may be too long to increase productivity. Can fall.
The halosilane is a compound including a Si-H bond, RSiX 3 , R 2 SiX 2 , R 3 SiX And may be any one selected from the group consisting of a combination thereof. In each of RSiX 3 , R 2 SiX 2, and R 3 SiX, each of R is hydrogen, an alkyl group having 1 to 30 carbon atoms, a cycloalkyl group having 3 to 30 carbon atoms, an alkenyl group having 2 to 30 carbon atoms, and having 6 to 30 carbon atoms. Alkenyl group and any one selected from the group consisting of a combination thereof, at least one R is hydrogen, X is a halogen atom.
The halosilane is specifically dichlorosilane, methyl dichlorosilane, ethyl dichlorosilane, ethyl diiodosilane, ethyl difluorosilane, dichloro monofluorosilane, propyl dibromosilane, isopropyl dichlorosilane, isobutyl dichlorosilane, iso Amyl dichlorosilane, benzyl dichlorosilane, propenyl dichlorosilane, naphthyl dichlorosilane, phenyldichlorosilane, difetyl chlorosilane, methyl ethyl chlorosilane, vinyl methyl chlorosilane, phenyl methyl chlorosilane, dibenzyl chlorosilane, p-chloro Phenylmethyl chlorosilane, n-hexyl dichlorosilane, cyclohexyl dichlorosilane, dicyclohexylchlorosilane, di-isobutyl chlorosilane, p-tolyl dichlorosilane, di-p-tolyl chlorosilane, p-styryl dichlorosilane, It may be any one selected from the group consisting of ethynyl dichlorosilane and combinations thereof.
The basic solvent included in the mixed solvent may be included in a ratio of 1: 2 to 1:10 (mole number of halogen group elements in halosilane: mole number of basic solvent) based on the number of moles of halogen group elements included in the halosilane. It may be to be, preferably be included in a molar ratio of 1: 4 to 1: 6.
When using the basic solvent more than 10 times the number of moles of the halogen group contained in the halosilane, a small amount of the salt of the halosilane and the basic solvent may be produced, the yield may be lowered, by using an excess solvent There is a problem in that the cost is increased, and when used less than twice, the halogenated elements contained in the halosilanes do not produce a sufficient amount of basic solvent and salt, so that side reactions by unreacted halogenated elements may occur in subsequent reactions. have.
When the halosilane is added in the mixed solution preparation step, the temperature of the mixed solvent may be -40 to -1 ° C. When the halosilane is mixed with the mixed solvent in the above temperature range, the heat of reaction generated when salts are formed between the halosilane and the basic solvent can be controlled to prevent vaporization of the halosilane due to the heat of reaction.
The reaction solution preparing step is a step of preparing a reaction solution by reacting halosilane included in the mixed solution with ammonia added to the mixed solution. In the reaction solution preparation step, the ammonia is added to the reaction solution containing the salt to add ammonia decomposition reaction.
The ammonia of the reaction solution preparation step may be added in a molar ratio (halosilane: ammonia) of 1: 2 to 8 based on the halosilane.
In the ammonolysis, the ammonia may be dissolved in the mixed solvent to substitute a halogen atom or to form an ammonium halide salt. When the ammonia is added in a molar ratio of less than 2 based on the halosilane, the ammonia decomposition reaction may not be sufficiently performed. When the ammonia is added in a molar ratio of more than 8, the reaction time increases and the amount of raw materials used increases. The cost can be increased and the acid catalyst action by the ammonium chloride salt in the reaction solution can be increased due to the use of excess ammonia.
The reaction solution preparing step may be made at a temperature of -42 to -30 ℃ at normal pressure (about 1 atm) for at least 3 hours, preferably for 3 hours to 7 hours. If the ammonolysis time is less than 3 hours in the reaction solution production step, the ammonolysis reaction may not be sufficient, and if the time exceeds 7 hours, the reaction may hardly occur and the cost may increase. have.
The reaction in the reaction solution production step may further comprise an organic solvent that does not affect the ammonolysis reaction. As the organic solvent which does not affect the ammonolysis reaction, any one selected from the group consisting of aliphatic hydrocarbons, alicyclic hydrocarbons, aromatic hydrocarbons, and combinations thereof may be used.
The aliphatic hydrocarbon may be, for example, any one selected from the group consisting of heptane, octane, nonene, decane, undecane, dodecane, tetradecane and combinations thereof. The alicyclic hydrocarbon may be, for example, any one selected from the group consisting of cyclohexane, methylcyclohexane, and combinations thereof. The aromatic hydrocarbon may be, for example, any one selected from the group consisting of toluene, xylene, ethylbenzene, benzene, and combinations thereof.
Generally, the ammonolysis reaction is exothermic and should be added slowly when the halosilane is added to the solvent. However, in the case of using the mixed solvent of the present invention, there is a control effect of the heat of reaction, so that the rate of ammonia injecting into the reaction solution may not be reduced, and the heat of reaction generated in the ammonolysis reaction can also be controlled within an appropriate range, thereby improving productivity and Reproducibility can be improved.
In the reaction solution preparation step, an ammonium chloride salt is formed by the ammonolysis reaction. The ammonium chloride salt may be present in a solid state in an inert solvent included in the mixed solvent to minimize acid catalysis of the ammonium ammonium salt, to minimize ammonia substitution of Si-H bonds of polysilazane, and to terminate the ends of Si-H 3 . To prepare a polysilazane containing a lot.
The reaction filtrate preparation step is to remove the salt from the reaction solution to prepare a reaction filtrate. The salt can be removed by a conventional method, for example by using a filter.
After the reaction filtrate preparation step may be optionally added to ammonia before the polysilazane solution production step. In general, the chloride of unreacted halosilane may remain after the polymerization reaction of halosilane and ammonia, which affects shrinkage as well as particle problems in preparing polysilazane solution. Therefore, in order to completely remove the chloride of the unreacted halosilane, additional ammonia is required.
The addition of ammonia is performed by cooling the reaction filtrate to −30 to 0 ° C., and then adding ammonia: addition in a molar ratio of 1: 0.01 to 1: 0.5 with respect to ammonia added in the reaction solution preparation step. Ammonia). When the amount of the added ammonia is less than 0.01 molar ratio, the effect of removing the unreacted chloride may be insignificant, and when the amount exceeds 0.5 molar ratio, the cost may increase due to the use of unnecessary ammonia.
In addition, after the addition of the ammonia can be carried out a low temperature or high temperature reaction at -20 ℃ to 100 ℃. When the reaction temperature is less than -20 ℃ may be a long reaction time due to low reactivity, when the reaction temperature is higher than 100 ℃ may increase the molecular weight of polysilazane. The added ammonia can be removed by a reduced pressure with a rotary pump after the low temperature or high temperature reaction.
The method for preparing polysilazane may further include a polymerization step after the reaction filtrate preparation step and before the polysilazane solution preparation step.
The polymerization step is a step of polymerizing the reaction filtrate prepared in the reaction filtrate preparation step for a reaction time of 6 to 300 hours at a reaction temperature of 40 to 120 ℃.
The reaction temperature may be 40 to 120 ° C, may be 60 to 120 ° C, may be 80 to 100 ° C. When the reaction temperature is less than 40 ℃ polymerization rate is too slow to decrease the productivity, when the reaction temperature is more than 120 ℃ can be difficult to control the molecular or gelation can proceed quickly.
The reaction time may be 6 to 300 hours, and may be 24 to 248 hours. By appropriately adjusting the reaction time, polysilazane having a molecular weight suitable for forming an insulating film can be produced. When the reaction time is less than 6 hours, the molecular weight of the polysilazane is too small to increase the volatilization during coating, and if it exceeds 300 hours, the stability of the polysilazane may be reduced.
When the reaction filtrate is polymerized at a reaction temperature of 40 to 120 ° C. for a reaction time of 6 to 300 hours, polysilazane having excellent stability may be prepared while having a high ratio of SiH 3 to SiH + SiH 2 .
The polysilazane solution preparation step is to remove the basic solvent from the reaction filtrate.
The removal of the basic solvent may be performed by a conventional method utilized for removing the solvent, and may be removed using a rotary pump.
The polysilazane prepared by the method for producing polysilazane may further be used as a polysilazane solution for forming an insulating film further including a coating solvent.
The coating solvent may be suitably used in consideration of storage stability, drying rate of the coating liquid, and the like, and preferably an organic solvent having a boiling point of 50 to 200 ° C may be used. For example, aliphatic compounds, saturated hydrocarbon compounds, ethers, esters, ketones and the like can be used, and specifically benzene, toluene, xylene, ethylbenzene, diethylbenzene, trimethylbenzene, triethylbenzene, cyclohexane, cyclohexene , Decahydronaphthalene, dipentene, pentane, hexane, heptane, octane, nonane, decane, ethylcyclohexane, methylcyclohexane, cyclohexane, cyclohexene, p-mentane, dipropyl ether, dibutyl ether, anisole, acetic acid Any one selected from the group consisting of butyl, amyl acetate, methyl isobutyl ketone and combinations thereof can be used.
After the polysilazane solution is prepared, a process of selectively adding ammonia may be performed. Even after preparing the polysilazane solution, chloride of unreacted halosilane may remain after the polymerization reaction of halosilane and ammonia, which affects not only particle problems but also shrinkage in preparing the polysilazane solution. Therefore, in order to completely remove the chloride of the unreacted halosilane, additional ammonia is required. The addition of the ammonia may be more effective to remove unreacted halosilane after proceeding to prepare the polysilazane solution.
The addition process of the ammonia is cooled to -30 to 0 ℃ polysilazane solution, and 1: 1: 1 to 1: 0.5 molar ratio relative to the ammonia added in the reaction solution production step (ammonia: Additional ammonia). When the amount of the added ammonia is less than 0.01 molar ratio, the effect of removing the unreacted chloride may be insignificant, and when the amount exceeds 0.5 molar ratio, the cost may increase due to the use of unnecessary ammonia.
In addition, after the addition of the ammonia can be carried out a low temperature or high temperature reaction at -20 ℃ to 100 ℃. When the reaction temperature is less than -20 ℃ may be a long reaction time due to low reactivity, when the reaction temperature is higher than 100 ℃ may increase the molecular weight of polysilazane. The added ammonia can be removed by a reduced pressure with a rotary pump after the low temperature or high temperature reaction.
In general, the polysilazane may be filtered and washed several times to remove the ammonium salt in the process of preparing polysilazane. However, according to the method of the present invention, polysilazane may be obtained without additional washing process and the yield may not be reduced. .
In addition, in the process of manufacturing the conventional polysilazane it is necessary to remove the anhydrous liquid ammonia under a pressurized state, this pressure removal process increases the risk and inconvenience of the manufacturing process. However, in the present invention, since anhydrous liquid ammonia can be removed by introducing an inert gas into the reaction solvent after the reaction, the risk and inconvenience of the manufacturing process can be reduced.
Polysilazane solution according to another embodiment of the present invention can be prepared by the method for producing the polysilazane solution. The polysilazane solution prepared by the method for preparing the polysilazane solution may reduce the shrinkage rate generated during coating to minimize tensile stress and thereby suppress bit line cracking and voids.
The polysilazane solution comprises polysilazane having an area ratio of the SiH 3 peak to the total area of SiH and SiH 2 peaks on the 1 H-NMR spectrum of 0.56 to 0.75. The polysilazane solution may include polysilazane having an area ratio of the SiH 3 peak to the total area of the SiH and SiH 2 peaks on the 1 H-NMR spectrum of 0.63 to 0.75.
If the area ratio of the SiH 3 peak to the total area of the SiH and SiH 2 peaks on the 1 H-NMR spectrum forms an insulating film using a polysilazane solution containing polysilazane having an area ratio of 0.56 to 0.75, It is possible to form a dense membrane and to prevent shrinkage of excess ammonia by preventing it from escaping.
The polysilazane may have a weight average molecular weight in terms of styrene of 3000 to 6000 or 3000 to 4500. When the polystyrene reduced weight average molecular weight of polysilazane is less than 3000, the content of volatilized components during coating of the insulating film is increased to form a relatively low-density insulating film, which deteriorates the mechanical properties of the insulating film and bakes after spin coating. When the resistance to cracks may be lowered at a time, and if it exceeds 6000, it may not penetrate well between the wiring and the electrode having a large aspect ratio due to the increase in viscosity, thereby forming a plurality of cavities in the insulating film. The properties may be lowered and also the stability of the polysilazane solution may be reduced.
Polysilazane included in the polysilazane solution includes a polysilazane structure represented by the following formula (1).
[Formula 1]
In Formula 1, n is an integer of 1 to 20, wherein R 1 to R 3 are each independently selected from the group consisting of hydrogen, a hydrocarbon group of 1 to 20 carbon atoms and a silyl group containing a hydrocarbon group of 1 to 20 carbon atoms One, preferably R 1 to R 3 may be any one selected from the group consisting of hydrogen, a hydrocarbon group of 1 to 10 carbon atoms and a silyl group containing a hydrocarbon group of 1 to 10 carbon atoms, more preferably R Each of 1 to R 3 may be independently selected from hydrogen, a hydrocarbon group having 1 to 6 carbon atoms, and a silyl group containing a hydrocarbon group having 1 to 6 carbon atoms.
The hydrocarbon group includes an alkyl group, an alkenyl group, a cycloalkyl group, a cycloalkenyl group, an aryl group, and an arylalkyl group. The hydrocarbon group-containing silyl group is one to three hydrocarbon groups bonded to Si.
The polysilazane of the present invention may be a polysilazane having a structure of linear, cyclic, crosslinked structure and combinations thereof, and may be a mixture thereof.
The method for preparing the polysilazane solution of the present invention and the polysilazane solution prepared by using the same may reduce the shrinkage rate when applied with an insulating film, such as a coating solution for semiconductor gap fill, thereby minimizing tensile stress and cracking of the bit line BL ( It is possible to suppress delamination and generation of voids.
1 is a 1 H-NMR graph of the polysilazane A prepared in Reference Example 1. FIG.
Hereinafter, embodiments of the present invention will be described in detail so that those skilled in the art can easily practice the present invention. The present invention may, however, be embodied in many different forms and should not be construed as limited to the embodiments set forth herein.
<Synthesis Example>
Reference Example 1
A mixed solvent was prepared by mixing 2 L (24.7 mol) of pyridine and 1 L (5.9 mol) of dibutyl ether while maintaining the temperature at -10 ° C. 200 g (2 mol, number of moles of chloride included = 4 mol) of dichlorosilane was added to the mixed solvent, followed by stirring to prepare a mixed solution. After cooling the mixed solution to −20 ° C., 270 g (15.9 mol) of ammonia was added slowly, and the mixed solution containing the ammonia was reacted for 4 hours to prepare a reaction solution.
The reaction filtrate in which the salt generated in the reaction solution was removed using a filter was reacted at 100 ° C. for 24 hours.
After completion of the reaction of the reaction filtrate, about 90% by weight of pyridine was removed by using a rotary pump, and 200 g (1.5 mole) of dibutyl ether was added to the reaction filtrate from which the pyridine was removed, and then residual pyridine was removed by a rotary pump. .
The pyridine-free reaction filtrate was diluted with 300 ml (1.8 mol) of dibutyl ether and filtered through a 0.05 μm filter to prepare a polysilazane solution.
The polystyrene reduced weight average molecular weight of polysilazane A contained in the polysilazane solution prepared by Example 1 was 3500.
1 H-NMR graph of the prepared polysilazane A is shown in FIG.
Example 1
A mixed solvent was prepared by mixing 2 L (24.7 mol) of pyridine and 1 L (5.9 mol) of dibutyl ether while maintaining the temperature at -10 ° C. 200 g (2 mol, number of moles of chloride included = 4 mol) of dichlorosilane was added to the mixed solvent, followed by stirring to prepare a mixed solution. After cooling the mixed solution to −20 ° C., 270 g (15.9 mol) of ammonia was added slowly, and the mixed solution containing the ammonia was reacted for 4 hours to prepare a reaction solution.
1.59 mol of ammonia was further added to the reaction filtrate from which the salt formed in the reaction solution was removed by using a filter, and reacted at -10 ° C for 1 hour, and then reacted at 100 ° C for 24 hours.
After the reaction of the reaction filtrate was completed, about 90% by weight of pyridine was removed by using a rotary pump, and 200 g (1.5 mol) of dibutyl ether was added to the reaction filtrate from which the pyridine was removed, and then residual pyridine was removed by a rotary pump. .
The pyridine-free reaction filtrate was diluted with 300 ml (1.8 mol) of dibutyl ether and filtered through a 0.05 μm filter to prepare a polysilazane solution.
The polystyrene reduced weight average molecular weight of polysilazane B contained in the polysilazane solution prepared by Example 1 was 3500.
Example 2
The reaction filtrate was prepared in the same manner as in Example 1, and the reaction filtrate was reacted at 100 ° C. for 24 hours. The reaction solution was prepared in the same manner as in Example 1 to prepare a polysilazane solution, an additional 1.59 moles of ammonia was added to the polysilazane solution and reacted at low temperature for 1 hour, followed by reaction at 100 ° C for 1 hour. Polysilazane solution was prepared.
The polystyrene reduced weight average molecular weight of polysilazane C contained in the polysilazane solution prepared by Example 2 was 3600.
Example 3
A reaction filtrate was prepared in the same manner as in Example 1, and 1.59 mol of ammonia was further added to the reaction filtrate and reacted at low temperature for 1 hour, followed by reaction at 100 ° C. for 24 hours. The reaction solution was prepared in the same manner as in Example 1 to prepare a polysilazane solution, an additional 1.59 moles of ammonia was added to the polysilazane solution and reacted at low temperature for 1 hour, followed by reaction at 100 ° C for 1 hour. Polysilazane solution was prepared.
The polystyrene reduced weight average molecular weight of polysilazane D contained in the polysilazane solution prepared by Example 3 was 3700.
Comparative Example 1
A polysilazane solution was prepared in the same manner as in Example 1 except that dibutyl ether was not used as a mixed solvent, only 2 L (24.7 mol) of pyridine was used as a solvent, and the reaction temperature of the reaction filtrate was 60 ° C. .
The polystyrene reduced weight average molecular weight of polysilazane E contained in the polysilazane solution prepared by Comparative Example 1 was 5600.
Comparative Example 2
Polysilazane solution was prepared in the same manner as in Example 1 except that pyridine was not used as the mixed solvent and only 2 L (11.7 mol) of dibutyl ether was used as the solvent.
The polystyrene reduced weight average molecular weight of polysilazane F contained in the polysilazane solution prepared by Comparative Example 2 was 1800.
<Physical Property Evaluation of Polysilazane>
Each of the solutions containing polysilazane synthesized in Reference Examples, Examples, and Comparative Examples of the Synthesis Example was applied as a composition for gapfill to evaluate physical properties.
5 ml of the semiconductor gap fill compositions of the Reference Examples, Examples and Comparative Examples were added dropwise to a silicon wafer (substrate) having a trench having a width of 32 nm and an aspect ratio of 10 or more, and a coating film was formed by spin coating.
The coating film was heated at 140 ° C. for 120 seconds to remove dibutyl ether as a solvent and to form a polysilazane film filling the trench.
The substrate was sequentially heated up to 900 ° C. and heated for 30 minutes to convert the polysilazane film into a silicon oxide film.
After the silicon oxide film was chemically mechanically polished using a ceria slurry, the substrate was immersed in an aqueous solution of buffered oxide etchant (BOE) for 1 minute and then dried to prepare a semiconductor device.
The reference examples, examples and comparative examples were observed and measured in the shrinkage rate and the presence of internal pores of the composition for the gap fill is shown in Table 1 below. The shrinkage rate was measured based on the film thickness change after the annealing process as compared to the film thickness in the prebaked state.
Input frequency
Referring to Table 1, it can be seen that when using the polysilazane according to the embodiments it is excellent in both the shrinkage rate and the internal pore generation compared to the reference example and the comparative examples.
In addition, it can be confirmed through the above examples and comparative examples that the effect of reducing the shrinkage rate can be obtained only when additional ammonia is added to the polysilazane synthesized using the mixed solvent.
Although the preferred embodiments of the present invention have been described in detail above, the scope of the present invention is not limited thereto, and various modifications and improvements of those skilled in the art using the basic concepts of the present invention defined in the following claims are also provided. It belongs to the scope of rights.
Claims (9)
Preparing a reaction solution by adding ammonia to the mixed solution and reacting the halosilane in the mixed solution with the ammonia added to the mixed solution;
Removing a salt from the reaction solution to prepare a reaction filtrate;
Removing the basic solvent from the reaction filtrate to prepare a polysilazane solution; And
Method of producing a polysilazane solution comprising the step of adding ammonia to the reaction filtrate or the polysilazane solution.
The step of adding the ammonia is a molar ratio of 1: 0.01 to 1: 0.5 with respect to the ammonia added in the step of preparing the reaction solution (Ammonia: reaction filtrate or polysilazane solution added in the reaction solution preparation step) Ammonia) is a method for producing a polysilazane solution.
After the step of introducing the ammonia, the method of producing a polysilazane solution further comprises the step of reacting the reaction filtrate or the polysilazane solution to which the ammonia is added at -20 to 100 ℃.
Method of producing a polysilazane solution further comprises the step of polymerizing the reaction filtrate at 40 to 120 ℃ for 6 to 300 hours.
The inert solvent is a method for producing a polysilazane solution containing at least one of dibutyl ether, xylene, toluene, ethylbenzene and benzene.
Wherein said basic solvent comprises at least one of pyridine, triazine and triethylamine.
The step of introducing the ammonia is a method of producing a polysilazane solution is performed between the step of preparing the reaction filtrate and the step of preparing the polysilazane.
The step of introducing the ammonia is a method for producing a polysilazane solution is carried out after the step of producing the polysilazane.
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| US9902873B2 (en) | 2014-05-26 | 2018-02-27 | Samsung Sdi Co., Ltd. | Composition for forming silica based layer, and method for manufacturing silica based layer |
| US9957418B2 (en) | 2015-05-15 | 2018-05-01 | Samsung Sdi Co., Ltd. | Composition for forming silica layer, method for manufacturing silica layer, and silica layer |
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| CN103910885A (en) | 2012-12-31 | 2014-07-09 | 第一毛织株式会社 | A process of preparing a gap filler agent, a gap filler agent prepared using same, and a method for manufacturing semiconductor capacitor using the gap filler agent |
| KR101599952B1 (en) * | 2012-12-31 | 2016-03-04 | 제일모직 주식회사 | Methods of producing polymers and compositions for forming silica insulation films |
| US10316216B2 (en) | 2016-08-31 | 2019-06-11 | Samsung Sdi Co., Ltd. | Composition for forming silica layer, and silica layer |
| US10647578B2 (en) | 2016-12-11 | 2020-05-12 | L'Air Liquide, Société Anonyme pour l'Etude et l'Exploitation des Procédés Georges Claude | N—H free and SI-rich per-hydridopolysilzane compositions, their synthesis, and applications |
| TWI799516B (en) | 2018-02-21 | 2023-04-21 | 法商液態空氣喬治斯克勞帝方法研究開發股份有限公司 | Perhydropolysilazane compositions and methods for forming oxide films using same |
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| JPH05345826A (en) * | 1991-12-04 | 1993-12-27 | Tonen Corp | Modified polysilazane and its production |
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| KR101056838B1 (en) | 2010-10-15 | 2011-08-12 | 테크노세미켐 주식회사 | Polysilazane solution and method of manufacturing the same |
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| KR970007491B1 (en) * | 1993-05-14 | 1997-05-09 | 한국과학기술연구원 | Polysilaxane and the manufacture thereof |
| KR101056838B1 (en) | 2010-10-15 | 2011-08-12 | 테크노세미켐 주식회사 | Polysilazane solution and method of manufacturing the same |
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| US9902873B2 (en) | 2014-05-26 | 2018-02-27 | Samsung Sdi Co., Ltd. | Composition for forming silica based layer, and method for manufacturing silica based layer |
| US9957418B2 (en) | 2015-05-15 | 2018-05-01 | Samsung Sdi Co., Ltd. | Composition for forming silica layer, method for manufacturing silica layer, and silica layer |
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