JP3490604B2 - Method for producing quaternary ammonium base type semiconductor surface treating agent - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION [0001] BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to the manufacture of semiconductor devices.
Cleaning of semiconductor substrate surface in oxidation / diffusion process
Of resist used in semiconductor photographic etching process
As a developer and stripper, and for etching semiconductor substrates
And CMP in the smoothing process of the semiconductor substrate.
(Chemical mechanical polish) polishing liquid and its CMP
Fourth amplifier used as a post-processing cleaning liquid after smoothing
MONIUM BASE-TYPE SEMICONDUCTOR SURFACE TREATMENT AND PROCESS FOR PRODUCING THE SAME
I do. [0002] 2. Description of the Related Art Conventionally, in these technical fields,
Is tetramethylammonium as a semiconductor surface treatment agent
Hydroxide (TMAH) or trimethyl (hydroxy
(Shiethyl) ammonium hydroxide (choline)
Quaternary ammonium bases are mainly used,
These quaternary ammonium bases are organic alkali compounds.
Contain alkali metals such as sodium and potassium
Extremely small amount of metal-free semiconductor surface treatment agent
It has great features. And the details are
No. 53-20376, No. 53-20377,
JP-B-55-40133 and JP-B-56-3409
No. 0 (semiconductor surface cleaning action)
Nos. 20376 and JP-B 63-2427
(Development and stripping action of resist), Tokiko 56-40
No. 976 and Japanese Patent Publication No. 56-53211 (half)
Etching action of conductor base). By the way, in recent semiconductor integrated circuits,
The progress of miniaturization has been remarkable, with 64 MDRAM, 256
Design dimensions of next-generation devices, such as MDRAM
The method has been made to a level of around 0.2 μm. About this
At the miniaturization level of, of course, short wavelengths such as excimer
Exposure method is required, and the resist material
An amplification system is needed. [0004] With respect to this chemically amplified resist,
For example, the following reaction formula (6) Embedded image As shown in the figure, a small amount of acid (H⁺) Touch
The acid-decomposable group (Y) is eliminated by a medium reaction and alkali-soluble
Dissolution of the resist progresses due to the mechanism
Achieving a level of resolution close to the exposure wavelength of Shima
There is a big feature in this point. However, this chemically amplified resist
There is also a problem with the
In between, it is easy to be affected by the air atmosphere,
Pattern control is insufficient and patterning reproducibility
Phenomena such as becoming scarce occur. [0006] This problem is caused by the trace amount contained in the atmosphere.
Caused by contamination with basic substances such as
On the resist surface⁺Resist is deactivated
Poor pattern shape (e.g. hardened surface, fine pattern
Such as a phenomenon that the pattern is not developed). And
When this phenomenon occurs, the dimensions of 0.2 μm level
Control becomes difficult and the excimer lithography system
The application of the body makes no sense. [0007] A small amount of amine-based air floating in the atmosphere
The sources of play objects are mainly cleaning liquids on semiconductor surfaces and development
Fourth solution such as TMAH and choline used as liquid
Ammonium base or RCA treatment solution (SC-1, NH_Three−
H_TwoO_Two-H_TwoO: 1: 6 mixture, W. Kern, RCA R
eview31, p187 (1970))_FourOH etc.
It is. And these processing liquids have a temperature of 60 to 80 ° C.
Is often used in semiconductor manufacturing processes.
It is a source of amine contamination at present,
In purifying the miniaturization of body elements, clean room air
It is extremely important to eliminate this amine suspension from inside
Has been a challenge and the fundamental solution
Development of treatment liquid for non-metallic semiconductors with little decomposition
Has been requested. Recently, the level of miniaturization has been increased to 256.
As MDRAMs and 1GDRAMs become available, STI (Sh
allow trench isolation) structure, DTI (Deep trench)
Isolation) For fine trench formation with structure and CMP
Process such as planarization of the semiconductor element surface
ing. And in these manufacturing processes,
Improving the cleaning performance at the minute openings is the key to improving the device yield.
More and more important in terms of surface
Development of non-metallic semiconductor processing solutions with excellent performance
ing. In particular, the surface roughness of the side wall of the trench minute opening is low.
Reduction agent, surface cleaning agent as post-CMP treatment, and
As a CMP polishing solvent, it has higher performance than conventional processing agents.
What is needed is development. By the way, it has been conventionally used as a semiconductor processing agent.
Choline is known to have the chemical structure "-CH_TwoCH
_TwoHas "OH" group and is more surface permeable than TMAH etc.
Is high, but the degree of decomposition of free amine
Is relatively large, and a surface treatment
Is not always enough. Also, the current
Choline is used in the production of secondary glycol such as polyethylene glycol.
Organisms are contained in a certain proportion (Japanese Patent Publication No. 63-2
No. 427), how much the above structural difference is
It is not always clear whether they are involved in the purification properties. [0010] The present invention is based on this background.
It was made based on the purpose
Is a better semiconductor surface treatment agent instead of choline
It has excellent storage stability and surface permeability,
Decomposition of free amines adapted to laffy production line
A new half of the quaternary ammonium hydroxide base type with very little
An object of the present invention is to provide a conductor surface treatment agent and a method for producing the same. [0011] That is, the present invention provides an
The following general formula (1) as an active ingredient Embedded image (Where R₁~ R_ThreeRepresents an alkyl group having 1 to 4 carbon atoms
And m and n are integers of 1 to 6, and x is 1 to
6 is an integer of 6)
Quaternary ammonium base type semiconductor surface treatment agent. Further, the present invention provides the following general formula (2) Embedded image (Where R₁~ R_ThreeRepresents an alkyl group having 1 to 4 carbon atoms
Trialkylamine represented by the following general formula:
(3) X- (C_mH_2mO)_x-C_nH_2nOH (3) (Where X represents a halogen atom, and m and n are 1 to
6 and x is an integer of 1 to 6).
Halogenated alkoxy having a halogen atom at the terminal
Quaternary ammonium halides
Quaternary ammonium halideWater soluble
liquidIs treated with an anion exchange resin, and is represented by the above general formula (1).
Quaternary ammonium hydroxideAqueous solution, and then
The above hydroxyl in an electrolytic cell using a cation exchange membrane as the diaphragm
Of aqueous solution of quaternary ammonium fluoride4th Ammo
This is a method for producing a silicon-based semiconductor surface treatment agent. Further, the present invention provides a compound represented by the above general formula (2).
1 mole of trialkylamine usedAgainstAlkyleneo
Quiside1.1 to 7 moles obtained by reactingThe following general
Equation (4) Embedded image (Where R₁~ R_ThreeIs the same as above, and m is 2 to 6
And x is 1 or 2)
Quaternary ammonium hydroxideAqueous solution of choline and po
Quaternary ammonium base type containing lalkylene glycol
It is a semiconductor surface treatment agent. Further, the present invention relates to a method for preparing
Having 2 to 6 carbon atoms0.1-5mo
Obtained by reactingThe following general formula (5) Embedded image (Where R₁~ R_ThreeIs the same as above, and m is 2 to 6
And y is 0 or 1.)
Quaternary ammonium hydroxideAqueous solution of
Quaternary ammonium base type semi-conductors containing alkylene glycol
It is a body surface treatment agent. [0015] Quaternary ammonium base type semiconductor table of the present invention
Hydroxide contained as an active ingredient in the surface treatment agent
As for the quaternary ammonium chloride, the compound represented by the general formula (1)
And the substituent R₁~ R_ThreeIs an alkyl group having 1 to 4 carbon atoms (alternating
May be the same or different).
And n is an integer of 1 to 6, and x is an integer of 1 to 6
Any compound may be used, but from the viewpoints of production and economics,
Preferably the substituent R₁~ R_ThreeIs a methyl group, an ethyl group, n
An alkyl group such as a propyl group, wherein m and n are 2 to 2
And x is 1 or 2. Further, the quaternary ammonium base type semi-organic compound of the present invention
The conductor surface treating agent is basically a hydroxylated compound represented by the general formula (1):
Tetraammonium is usually 0.01 to 50% by weight, preferably
Is used as an aqueous solution containing 0.1 to 30% by weight.
It is. Furthermore, the quaternary ammonium base type semiconductor table of the present invention
For surface treatment agents, for example, improvement of surface wettability and etching
Anion for fine control of grate
Add a non-ionic or non-ionic surfactant or hydrogen peroxide
Is also good. The quaternary ammonium hydroxide of the general formula (1) of the present invention
As a method for producing nickel, typically,
A trialkylamine represented by the formula (2);
Halogen having a halogen atom at the terminal represented by (3)
Reaction with activated alkoxy alcohols,
At least equimolar to the trialkylamine represented by the formula (2)
A method of reacting ethylene oxide can be used. Here, the trialkylamide of the general formula (2)
Specific examples of trimethylamine and ethyldiamine
Methylamine, diethylmethylamine, triethylamido
, Tri-n-propylamine, tri-n-butylamine, etc.
Are preferred, and the compound represented by the general formula (3)
Specific examples of the halogenated alkoxy alcohols include:
Is chloromethoxymethanol, chloroethoxyethanol
Chloro, n-propoxy n-propanol, chloro
Isopropoxyisopropanol, chloroethoxyeth
Xyethanol, bromomethoxymethanol, bromoe
Preferred is toxicethanol, iodoethoxyethanol, etc.
It is mentioned as a thing. The trialkylamine of the general formula (2)
Reaction with halogenated alkoxy alcohols of formula (3)
In the method of causing
Are reacted using a solvent that dissolves both as a solvent.
The quaternary ammonium halide of the reaction product is separated
Then, the quaternary ammonium halide is dissolved in pure water.
Quaternary ammonium hydroxide
The desired product is obtained as an aqueous solution of As a solvent suitable for use for this purpose
Is, for example, methyl alcohol, ethyl alcohol, n-
Alkali such as propyl alcohol and isopropyl alcohol
Coals, benzene, toluene, xylene, diethyl
Ether and petroleum ether can be exemplified. this
Among these solvents, methyl alcohol, ethanol, etc.
Alcohols are economical because raw materials and products have good solubility.
It is preferable because it is. The trialkylamine and halogen
Reaction Conditions for Reacting with Alkoxy Alcohols
Is not particularly limited, but is preferably
Is a reaction vessel using an autoclave or the like, and a reaction temperature of 1
20 ° C or lower, preferably 60 to 100 ° C, reaction pressure normal pressure
-10kg / cm^TwoAnd a reaction time of 1 to 8 hours.
Good. The quaternary ammonium hydroxide thus obtained is obtained.
For aqueous solutions of sodium, it is preferable to use positive electrodes as diaphragms.
Using an electrolytic cell with an on-exchange membrane, voltage about 5-50V
And current of about 1 to 50 A / dm^TwoDC voltage is applied under the condition of
For electrolytic treatment, thereby obtaining Cl 2⁺, NO_Three ^-, SO
_Four ^2-, Br^-, I^-, And also polyethylene glycol, etc.
In addition to removing impurities as much as possible, a predetermined concentration, for example,
0.01 to 50% by weight, preferably 0.1 to 30% by weight
Concentrate to quaternary ammonium hydroxide aqueous solution
Suitable as a treatment agent or convenient for handling such as transportation
Quaternary ammonium hydroxide aqueous solution of high concentration and high purity
I do. The trialkyl group represented by the general formula (2)
Equimolar or more, preferably 1.1 to 7 moles
, More preferably 2 to 5 moles of alkylene oxide
For producing quaternary ammonium hydroxide by reacting
Is a hydroxyl group having the general formula (4) wherein x is 1 or 2.
Preferred as a method for industrial production of quaternary ammonium
Things. According to this method, the reaction can be easily controlled.
Has the advantage of being economical. The trialkylamine has an equimolar or more
The method of reacting the alkylene oxide is, specifically,
In 0.01 to 35% by weight aqueous solution of trialkylamine
At a predetermined temperature, usually 5 to 100 ° C., preferably 10 to 100 ° C.
At a temperature of 70 ° C., a predetermined amount of alkylene oxide or
Of an aqueous solution of 0.01 to 1000 g / min, preferably 0.1 g / min.
Introduced at a rate of 01 to 100 g / min.
And / or unreacted trialkylamine or
Strips the kylene oxide and removes the desired hydroxyl
An aqueous tetraammonium solution is obtained. According to the method of the present invention, the general formula (1)
Aqueous solution of quaternary ammonium hydroxide with high purity and
Can be produced in high concentrations and can be obtained in this way
The aqueous solution of quaternary ammonium hydroxide of the present invention contains
By-products such as ethylene glycol and trialkylamine
Unreacted substances and impurities such as free amines generated by decomposition
Contains little or no halogens such as chlorine
Is extremely low in the content of conventional choline
In comparison, these by-products, unreacted materials, and other impurities
The weight can be significantly lower and the production stability
And reproducibility can be significantly improved. Further, the number of carbon atoms is 2 to 1 mol of choline.
6 alkylene oxides0.1 molAbove, preferably
0.1-5 mol, more preferably 0.5-3 mol
The method of producing quaternary ammonium hydroxide by
A quaternary ammonium hydroxide wherein y is 0 or 1 in the general formula (5);
Is a preferred method for industrial production of
You. In this method, too, the control of the reaction is easy and economical.
There is an advantage that there is. Reaction of this choline with an alkylene oxide
Specifically, a specific method is described in an aqueous solution of choline.
Temperature, usually 5-100 ° C, preferably 10-70 ° C
At a temperature, a predetermined amount of alkylene oxide or an aqueous solution thereof
To obtain the desired quaternary ammonium hydroxide aqueous solution.
You. [0028] DESCRIPTION OF THE PREFERRED EMBODIMENTS Hereinafter, Examples, Comparative Examples, and trials
Specific examples of preferred embodiments of the present invention will be described based on experimental examples.
explain. Embodiment 1 Trimethylamine 193 dissolved in 610 g of methanol
g (3.27 mol) and 2- (2-chloroethoxy) e
343 g (2.75 mol) of chill alcohol and methanol
In an autoclave, and the reaction temperature was 80
° C, reaction pressure 3.0 kg / cm^TwoAnd reaction time 6.5 hours
The reaction was performed under the following conditions. After the reaction is completed, the amount is reduced from the reaction mixture.
The solvent methanol and unreacted trimethyl alcohol
Mines and the like were removed to obtain 522 g of needle-like crystals of the reaction product.
Was. The obtained reaction product is dissolved in 21 kg of pure water.
Anion exchange after dissolving into aqueous solution and purifying to OH form
Resin (Amberlite IRA-400 manufactured by Organo)
Pass the aqueous solution through a column filled with 3.2 liters,
With a chlorine content of 26 ppm and a concentration of 1.01% by weightHydroxylation
2- (2-hydroxyethoxy) ethyltrimethylan
Aqueous solution of monium(DECH aqueous solution) 30 kg was obtained.
The chlorine content is measured by ion chromatography
And DECH for capillary electrophoresis
And quantified by neutralization titration. Next, a Teflon-made anode loaded with a graphite anode is used.
Anode compartment and stainless steel (SUS316L) cathode inserted
Between the Teflon cathode chamber
Exchange membrane (trade name: Nafion 324, manufactured by DuPont)
Prepare an electrolytic cell with a structure with
The DEC aqueous solution was circulated within the condition with a residence time of 25 seconds.
And 3 kg of pure water in the cathode chamber for a residence time of 50 kg.
Circulate under the condition of seconds, and apply a voltage of about 0 between the anode and the cathode.
~ 30V and current about 2.0A / dm^TwoDC voltage of 29
Electrolysis treatment by applying time, chlorine content 1ppm or less and
3.6 kg of a DECH aqueous solution having a concentration of 6.56% by weight was obtained.
Was. The resulting aqueous DECH solution is polyethylene glycol
Concentration is 500 ppm or less, and trimethyl alcohol
The min concentration was 0.5 ppm. Embodiment 2 Trimethylamine 174 dissolved in 447 g of methanol
g (2.94 mol) and 2- [2- (2-chloroethoxy)
B) ethoxy] ethyl alcohol 463 g (2.75 m
And 231 g of methanol in an autoclave.
, Reaction temperature 85 ° C, reaction pressure 2.8kg / cm^Twoas well as
The reaction was performed under the condition of a reaction time of 5 hours. After completion of the reaction, the reaction mixture was mixed in the same manner as in Example 1.
670 g of needle crystals of the reaction product were obtained from the compound,
Purified by ion exchange resin column, chlorine content 30ppm
And 2- [2- (2-hydroxide) having a concentration of 2.13% by weight.
Roxyethoxy) ethoxy] ethyltrimethylammonium
20.7 kg of a water solution (aqueous TECH solution) was obtained. The obtained TECH aqueous solution was used in the same manner as in Example 1 above.
In the same manner, an electrolytic treatment for 35 hours was performed to obtain a chlorine content of 1 p.
3. pm or less and 6.98 wt% concentration of DECH aqueous solution
3 kg were obtained. In addition, the obtained TECH aqueous solution is
If the ethylene glycol concentration is
The tilamine concentration was 0.4 ppm. Test Example 1 (Storage stability) DECH aqueous solution obtained in Examples 1 and 2 and TE
CH aqueous solution was diluted with pure water to obtain 4.6% by weight of D
An aqueous solution of ECH and an aqueous solution of TECH are prepared, and these D
ECH aqueous solution and TECH aqueous solution in a thermostat at 50 ° C
Storage and storage of trimethylamine over time
The changes were examined. Also used as a semiconductor processing agent
4.6% by weight choline aqueous solution (Tama Chemical Industry Co., Ltd.)
The same applies to the product name of TM-3)
Storage and storage of trimethylamine over time
The changes were examined. Table 1 shows the results. [0036] [Table 1] As is apparent from the results in Table 1, 30
After the passage of days, the amount of trimethylamine
Compared to the case of the aqueous solution, the aqueous DECH solution of the present invention is about 1
About / 10, about 1/100 for TECH aqueous solution
The amount of trimethylamine generated by decomposition during storage
Was confirmed to be extremely small. In addition,
Min odor is also less in the order of choline ≫ DEC ≥ TECH.
The DEC aqueous solution and the TECH aqueous solution of Examples 1 and 2
It is much more stable than phosphorous solution and chemically amplified
Semiconductor processing that is extremely advantageous in terms of the environmental atmosphere
It turned out to be an agent. Test Example 2 (Surface tension) DECH aqueous solution obtained in Examples 1 and 2 and TE
The CH aqueous solution is diluted with pure water to obtain 5.50% by weight D
Prepare ECH aqueous solution and 5.78 wt% TECH aqueous solution
And a CBVP surface tensiometer manufactured by Kyowa Interface Science Co., Ltd.
The surface tension at ℃ was measured and pure water, 2.38 wt% TMA
H solution and 5.00% by weight choline solution
did. Table 2 shows the results. [0039] [Table 2] As is clear from the results in Table 2, the choline water
The surface tension of the solution is almost equal to that of water or TMAH aqueous solution
Although no effect of lowering the surface tension was confirmed,
However, in the DEC aqueous solution and the TECH aqueous solution of the present invention,
The surface tension is clearly reduced, and fine openings in the semiconductor substrate
Of developing solution to penetrate into parts and fine resist pattern
There is an advantage for permeability and the like. Test Example 3 (resist dissolution characteristics) Product name: FH640 manufactured by Fuji Hunt Company as a positive resist
0L (coating thickness: 1.5 μm)
Use Nikon stepper NSR1505G3A for exposure.
Use the left axis to dissolve the resist in the unexposed area (um / min)
And the right axis indicates the minimum exposure (the resist
Plot the amount of exposure required to fully develop the
Was. Here, the energy unit of the exposure amount is
Expressed in “m.sec” which is the control display of the Tepper. Ma
In addition, the DEC of Example 1 for the dissolution characteristics of a positive resist
The concentration dependency of the H aqueous solution was examined, and 2.38 wt% TMAH was examined.
It was compared with an aqueous solution and a 5.0 wt% choline aqueous solution. The result
As shown in FIG. From the results shown in FIG. 1, the DECH of the first embodiment
The aqueous solution has a development dissolution characteristic at a concentration of around 3.25% by weight.
Is 2.38 wt% TMAH aqueous solution and 5.0 wt% choline
It has the same performance as the aqueous solution
Dissolution rate is as low as 0.05 μm / min.
When the resist profile is 2.38 wt% TMAH
It was of the same level as. Also, the DE of the first embodiment
CH solution is remarkable as fine lines and spaces
Resist footing phenomenon seen in
It showed a favorable trend. The aqueous DECH solution of Example 1 of the present invention
The concentration dependency on the solubility of the unexposed resist
Remarkably increases rapidly when the concentration of is more than 5.0% by weight.
Properties and relatively low compared to choline aqueous solution.
High resist stripping ability at high concentration
Was. This is because of the smell of DECH aqueous solution and choline aqueous solution.
From the measured data, the relationship between the concentration and the pH dependence
A phenomenon that is hard to imagine because it hardly changes
Ethoxy bond (-CH_TwoCH_Two
O-) differences are directly related to this phenomenon.
And one or more ethoxy bonds are present in the chemical structure.
The dependence of the solution concentration on the solubility
It is thought that will become stronger. Test Example 4 (Etching characteristics) The aqueous DECH solution obtained in Example 1 was diluted with pure water.
To prepare a 1.42% by weight aqueous DECH solution at room temperature (24 hours).
C) for a predetermined period of time to improve the etching characteristics of the exposed Si surface.
Examined. The result is the etching rate of the (100) Si exposed surface.
The rate was about 400 ° / min. The 1.42% by weight aqueous DECH solution
But naturally grown on the Si surface in the same way as the choline solution
Since the oxide film is etched, the natural acid
With low contamination while suppressing the growth of
Surface treatment is equivalent to that of a choline aqueous solution or TMAH aqueous solution.
Bell turned out to be possible. Test Example 5 (detergency) DECH aqueous solution obtained in Examples 1 and 2 and TE
CH aqueous solution is diluted with pure water to obtain 0.1% by weight of D
Prepare ECH aqueous solution and TECH aqueous solution, and add
Pure hydrogen peroxide was added at a ratio of 4% by weight,
Cleaning solution of Her (DEC cleaning solution and TECH cleaning solution)
Prepared. Also,⁶⁴HF solution with Cu2ppb added
The semiconductor wafer was immersed in for 10 minutes and then obtained
⁶⁴After rinsing the Cu-adsorbed wafer with ultrapure water and drying,
After that, release in a polypropylene wafer case for 24 hours.
The organic outgas generated from this wafer case
Further contaminates the wafer surface, causing organic contamination⁶⁴Cu adsorption
I prepared Eher. The above DEC cleaning solution or TECH cleaning solution is
Organic contamination used and prepared above⁶⁴7 Cu adsorption wafer
Washing was performed at 0 ° C. for 10 minutes. The result is that any wash
Liquid remains on the wafer surface⁶⁴Cu content is about
(3-4) x 10¹¹atom / cm^TwoAbout
Adsorbed on the surface⁶⁴About 30 to 40% of Cu amount is removed
It had been. Ultra-high purity peracid in 0.1% by weight choline aqueous solution
Preparation of choline washing solution by adding 4% by weight of hydrogen chloride
Then, the same cleaning test as described above was performed and compared. Result is,
What is DECH cleaning solution, TECH cleaning solution and choline cleaning solution?
They also show the same detergency, the aqueous DECH solution of the present invention and
TECH aqueous solution has detergency equivalent to choline aqueous solution
It has been found. Embodiment 3 Flush with reflux condenser and trimethylamine inlet tube
2- (2-chloroethoxy) dissolved in 500 g of pure water
343 g (2.75 mol) of xyl) ethyl alcohol
And set the flask in a water bath maintained at 80 ° C.
And the trimethylamine 23
7 g (3.27 mol) at a rate of 1 liter / min.
The reaction was conducted by introducing for an hour. After completion of the reaction, the reaction mixture was distilled under reduced pressure.
Trimethylamine and the like in the reaction are removed, and the resulting aqueous solution is
Purified by anion exchange resin column in the same manner as in Example 1.
And a chlorine content of 47 ppm and a concentration of 2.06% by weight.
19.9 kg of an ECH aqueous solution was obtained. Further, the obtained aqueous DECH solution was subjected to the above-described procedure.
Performed an electrolysis treatment for 30 hours in the same manner as in Example 1 and contained chlorine.
DECH aqueous solution with an amount of 1 ppm or less and a concentration of 5.2% by weight
4.6 kg were obtained. Also, the obtained aqueous DECH solution is
If the polyethylene glycol concentration is 500 ppm or less,
Limethylamine concentration was 0.5 ppm. Embodiment 4 343 g of 2- (2-chloroethoxy) ethyl alcohol
(2.75 mol) instead of 2- [2- (2-chloroethoxy)
463 g of (xy) ethoxy] ethyl alcohol (2.75)
Mol), except that TE was used in the same manner as in Example 3 above.
An aqueous CH solution was prepared. Obtained by purifying with an anion exchange resin column
19.8 kg of TECH aqueous solution has a chlorine content of 42 pp
m, the concentration was 2.23% by weight. Also, this TE
TEC obtained by electrolytic treatment (35 hours) of CH aqueous solution
The H2 aqueous solution (4.7 kg) has a chlorine content of 1 ppm or less.
The degree was 6.58% by weight. Also, the obtained TECH
The aqueous solution has a polyethylene glycol concentration of 500 ppm
Below, the trimethylamine concentration is 0.4 ppm.
Was. Examples 5 to 8 Trimethylamine 281.5 dissolved in 5640 g of pure water
g (4.76 mol) of ethylene oxide in 40
0 g (9.08 mol, Example 5), 555 g (12.6
1 mol, Example 6), 660 g (14.99 mol, practice
Example 7) and 776 g (17.61 mol, Example 8)
At a reaction temperature of 25 to 40 ° C and ethylene oxide.
2 hours each at 3.3 g / min side introduction speed
(Example 5) 2.7 hours (Example 6), 3.2 hours
(Example 7) and 3.7 hours (Example 8)
Was. The aqueous solution thus obtained was concentrated at a concentration of 5.
After adjusting to 0% by weight, capillary
Identified by electrophoresis. Also, gas chromatography analysis
By-product polyethylene contained in each aqueous solution
The amount of recall was measured. Table 3 shows the results. [0057] [Table 3] As is clear from the results shown in Table 3, the bird
The amount of ethylene oxide used for methylamine (anti-
As the molar ratio increases, DEC, TECH and
And the production ratio of PEG increases, and the reaction molar ratio is 2 or more.
Above, preferably at least 3 with DEC or TECH as the main component
Turns out to be a quaternary ammonium hydroxide base
did. The quaternary ammonium hydroxides of Examples 5 to 8
The aqueous solution of chromium is also different from those of Examples 1 and 2 above.
Almost the same but slightly different in its properties
Stability, surface tension, resist dissolution characteristics, etching characteristics
And amine cleaning at room temperature.
Example 5 which is slightly more than that of Examples 1 and 2
> Example 6> Example 7 ≫ Example 8
Much less than conventional choline solutions
Environmentally friendly for chemically amplified resist
It has been found to be an advantageous semiconductor treating agent. Examples 9 to 11 500 g of 15% by weight choline aqueous solution (75 g of pure choline,
0.619 mol) of ethylene oxide.
6 g (0.309 mol, Example 9), 40.7 g (0.
924 mol, Example 10), and 81.8 g (1.86
Mole, used in the ratio of Example 11), and the reaction temperature was 25-4.
0 ° C. and an ethylene oxide introduction rate of 1.0 g / min.
13.6 minutes each (Example 9), 40.7 minutes
(Example 10) and reaction for 81.8 minutes (Example 10)
I let it. The reaction product was analyzed by neutralization titration with aqueous choline solution.
Adjust with pure water to be 5.0% by weight in terms of liquid.
Was. In addition, quaternary ammonium hydroxide and ethylene glycol
(EG) is qualitatively and quantitatively determined by the GPC mode.
Analysis was performed by body chromatography. The results are shown in Table 4.
You. [0062] [Table 4] [0063] According to the present invention, compared with the conventional choline,
Has better storage stability and surface permeability,
Amines suitable for the fine lithography production line in Japan
Quaternary ammonium base with extremely low decomposition
New type of semiconductor surface treatment agent and its manufacturing method
be able to.

BRIEF DESCRIPTION OF THE DRAWINGS FIG. 1 shows DECH obtained in Examples 1 and 2.
FIG. 4 is a graph showing the concentration dependency of the aqueous solution and the TECH aqueous solution on the resist solubility.

────────────────────────────────────────────────── ─── Continued on the front page (51) Int.Cl. ⁷ Identification code FI H01L 21/027 H01L 21/304 622C 21/304 622 647Z 647 21/30 569E 572B (72) Inventor Yoshiro Ota Kawasaki City, Kanagawa Prefecture 3-22-9 Shiohama, Kawasaki-ku, Tama Chemical Industry Co., Ltd., Kawasaki Research Laboratories (72) Inventor Shunpei Shimizu 12-1, Ekimae Honcho, Kawasaki-ku, Kawasaki-shi, Kanagawa Prefecture Kawasaki Ekimae Tower Riverk 17th floor, Tama Chemical Industry Co., Ltd. (56) References JP-A-61-186351 (JP, A) JP-A-8-218191 (JP, A) (58) Fields investigated (Int. Cl. ⁷ , DB name) H01L 21/027, 21 / 304 H01L 21 / 306,21 / 308

Claims (1)

(57) [Claims] [Claim 1] The following general formula (2) (Wherein, R _{1 to} R ₃ represent an alkyl group having 1 to 4 carbon atoms), and X- (C _m H _2m O) _x -C _n represented by the following general formula (3). H _2n OH (3) (wherein, X represents a halogen atom, and m and n are 1 to
6, and x is an integer of 1 to 6) to react with a halogenated alkoxy alcohol having a halogen atom at a terminal to synthesize a quaternary ammonium halide. An aqueous solution of quaternary ammonium is treated with an anion exchange resin to obtain the following general formula (1): (Wherein, R _{1 to} R ₃ , m and n and x are the same as those described above), and then an electrolytic cell using a cation exchange membrane as a diaphragm. And subjecting the aqueous solution of quaternary ammonium hydroxide to electrolytic treatment.