JPH02143525A - Etchant preparation - Google Patents
Etchant preparationInfo
- Publication number
- JPH02143525A JPH02143525A JP29891288A JP29891288A JPH02143525A JP H02143525 A JPH02143525 A JP H02143525A JP 29891288 A JP29891288 A JP 29891288A JP 29891288 A JP29891288 A JP 29891288A JP H02143525 A JPH02143525 A JP H02143525A
- Authority
- JP
- Japan
- Prior art keywords
- chemical solution
- etching rate
- concentration
- solution
- etching
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 238000002360 preparation method Methods 0.000 title claims description 6
- 239000000126 substance Substances 0.000 claims abstract description 56
- 238000005530 etching Methods 0.000 claims abstract description 24
- 239000007788 liquid Substances 0.000 claims description 6
- 238000000034 method Methods 0.000 abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 abstract description 9
- 239000000463 material Substances 0.000 abstract description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 abstract 2
- 229910052681 coesite Inorganic materials 0.000 abstract 1
- 229910052906 cristobalite Inorganic materials 0.000 abstract 1
- 239000000377 silicon dioxide Substances 0.000 abstract 1
- 235000012239 silicon dioxide Nutrition 0.000 abstract 1
- 229910052682 stishovite Inorganic materials 0.000 abstract 1
- 229910052905 tridymite Inorganic materials 0.000 abstract 1
- 239000000243 solution Substances 0.000 description 40
- 238000006386 neutralization reaction Methods 0.000 description 9
- 238000004448 titration Methods 0.000 description 9
- 239000011550 stock solution Substances 0.000 description 7
- 239000003814 drug Substances 0.000 description 6
- 229940079593 drug Drugs 0.000 description 6
- 238000002156 mixing Methods 0.000 description 6
- 238000006243 chemical reaction Methods 0.000 description 5
- 235000012431 wafers Nutrition 0.000 description 5
- 239000002245 particle Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 3
- LDDQLRUQCUTJBB-UHFFFAOYSA-N ammonium fluoride Chemical compound [NH4+].[F-] LDDQLRUQCUTJBB-UHFFFAOYSA-N 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000001678 irradiating effect Effects 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- UNPLRYRWJLTVAE-UHFFFAOYSA-N Cloperastine hydrochloride Chemical compound Cl.C1=CC(Cl)=CC=C1C(C=1C=CC=CC=1)OCCN1CCCCC1 UNPLRYRWJLTVAE-UHFFFAOYSA-N 0.000 description 1
- 230000003213 activating effect Effects 0.000 description 1
- 238000005285 chemical preparation method Methods 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000000691 measurement method Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
Landscapes
- Weting (AREA)
Abstract
Description
【発明の詳細な説明】
［概要コ
エツチング液の調合方法に関し、
薬液のエッチレートを短時間で支定させるとともに、エ
ッチレートを正確に調節できる薬液調合方法を提供する
ことを目的とし、
エツチング用薬液に波長がｌｎｍ−１ｌ１００ｎの電磁
波を照射し、その後前記薬液により彼処Ｔｌ質をエツチ
ングしエッチレートを測定し、予め求められた前記薬液
と前記被処理物質のエッチレートの関係に基づいて、必
要により、薬液濃度を所定値に調節するように構成する
。[Detailed Description of the Invention] [Summary] The purpose of this invention is to provide a method for preparing a chemical solution that can stabilize the etch rate of a chemical solution in a short period of time and accurately adjust the etch rate. irradiate with electromagnetic waves having a wavelength of lnm-1l100n, and then etch the Tl material there with the chemical solution and measure the etch rate. , and is configured to adjust the concentration of the chemical solution to a predetermined value.
［産業上の利用分野］
本発明はエツチング液の調合方法に関するものであり、
さらに詳しく述べるならば半導体装置の構成材料である
Ｓｉなどの半導体、あるいは５ｉＯｚ、ＰＳＧ等の絶縁
膜をエツチングする薬液調合方法に関する。[Industrial Application Field] The present invention relates to a method for preparing an etching solution,
More specifically, the present invention relates to a chemical preparation method for etching a semiconductor such as Si, which is a constituent material of a semiconductor device, or an insulating film such as 5iOz or PSG.
ウェット処理工程に使用する薬液には、原液に含まれる
微小なパーティクルが混入しているか、あるいは原液と
水などとの混合時にパーティクルが混入する。かかる薬
液をそのままウェットプロセスに使用すると、薬品単位
量当たりの処理可能ウェハー数が少なくなり、薬液を早
期に廃却せざるを得す、歩留まりの低下を招く。The chemical solution used in the wet treatment process contains minute particles contained in the stock solution, or particles are mixed in when the stock solution is mixed with water or the like. If such a chemical solution is used as it is in a wet process, the number of wafers that can be processed per unit amount of chemical decreases, forcing the chemical solution to be disposed of early, resulting in a decrease in yield.
そこで、薬液は歩留まり向上のためパーティクルの低減
が必要とされ、フィルターによるパーティクル除去が行
なわれる。Therefore, it is necessary to reduce the number of particles in the chemical solution in order to improve the yield, and the particles are removed using a filter.
又、近年、ウェットプロセスの能率化のために、薬品原
液あるいは使用ずみ薬品を純水で所定濃度に調合し、予
め定められた処理ウェハー数の処理の完了後、薬液をエ
ツチングプロセスに自動的に供給する薬品の自動供給化
が要求されている。In addition, in recent years, in order to improve the efficiency of wet processes, chemical stock solutions or used chemicals are mixed with pure water to a predetermined concentration, and after a predetermined number of wafers have been processed, the chemical solution is automatically added to the etching process. Automatic supply of chemicals is required.
この薬品自動供給化技術の薬品調合においては、ウェッ
ト処理されるべきウェハーの大きさ、５ｉ０２などの絶
縁膜面績などの因子により薬品濃度を定める必要がある
。そして、調合後には所定濃度が得られているか確認を
する必要がある。In the chemical formulation of this automatic chemical supply technology, it is necessary to determine the chemical concentration based on factors such as the size of the wafer to be wet-processed and the surface quality of the insulating film such as 5i02. After blending, it is necessary to confirm whether a predetermined concentration has been obtained.
［従来の技術］
従来の半導体素子製造のウェット処理工程で用いられて
いるエツチング液のエッチレートは薬品濃度により管理
され、濃度は中和滴定または導電率で調整しいる。とこ
ろが薬品原液と純水の調合後、調合系の反応が容易に平
衡に達しないため、エッチレートにバラツキが生じ、調
整に長い時間を要した。[Prior Art] The etch rate of an etching solution used in a conventional wet processing process for manufacturing semiconductor devices is controlled by chemical concentration, and the concentration is adjusted by neutralization titration or conductivity. However, after mixing the chemical stock solution and pure water, the reactions in the mixing system did not reach equilibrium easily, resulting in variations in the etch rate and requiring a long time to adjust.
［発明が解決しようとする課題］
従って、薬液調合時、分析や反応の平衡のために、調合
後すぐには使用できず例えば−日以上の長時間待つとい
った問題を生じていた。[Problems to be Solved by the Invention] Therefore, when preparing a drug solution, due to analysis and reaction equilibrium, the drug cannot be used immediately after preparation, resulting in a problem of waiting for a long time, for example, - days or more.
一方、中和滴定や電気電動度測定により検出される薬液
のデータは調合直後から一定しており、データの安定の
ために一口もの民時間を必要とすることはない。On the other hand, the data of the chemical solution detected by neutralization titration or electromotor measurement is constant immediately after preparation, and no amount of private time is required to stabilize the data.
従って、中和滴定などにより、調合直後、薬液の濃度を
測定し、測定値が所定のものであったならば直ちにウェ
ットプロセスに薬液を供給する方法では、薬品の自動供
給化技術を実施するのは困難である。すなわち、次の処
理予定ウェハー用薬液の仕様は予想できるが、当該ウェ
ハーの処理開始時間が正確に予想できない；薬液の急速
な劣化など予期できない事態に対処できない：などの点
で自動供給への対応が困難である。Therefore, the method of measuring the concentration of a chemical solution immediately after preparation, such as by neutralization titration, and immediately supplying the chemical solution to the wet process if the measured value is a predetermined value, requires automatic chemical supply technology. It is difficult. In other words, although the specifications of the chemical solution for the next wafer to be processed can be predicted, the processing start time for the wafer cannot be predicted accurately; it is not possible to deal with unpredictable situations such as rapid deterioration of the chemical solution; is difficult.
本発明は調合された薬液のエッチレートを短時間で安定
させるとともに、エッチレートを正確に調節できる薬液
調合方法を提供することを目的とする。SUMMARY OF THE INVENTION An object of the present invention is to provide a method for preparing a chemical solution that can stabilize the etch rate of a prepared chemical solution in a short period of time and can accurately control the etch rate.
［課題を解決するための手段］
本発明は、エツチング用薬液に波長が１ｎｍ〜４００ｎ
ｍの電磁波を照射し、その後前記薬液により被処理物質
をエツチングしエッチレートを測定し、予め求められた
前記薬液と前記被処理物質のエッチレートの関係に基づ
いて、必要により、薬液濃度を所定値に調節することを
特徴するエツチング液調合方法である。[Means for Solving the Problems] The present invention provides an etching chemical solution having a wavelength of 1 nm to 400 nm.
irradiate with electromagnetic waves of m, then etch the substance to be treated with the chemical solution, measure the etch rate, and, if necessary, set the concentration of the chemical solution to a predetermined value based on the predetermined relationship between the etch rate of the chemical solution and the substance to be treated. This is a method for preparing an etching solution, which is characterized by adjusting the etching solution to a specific value.
第１図は、本発明の原理説明図である。図中１．２は薬
品原液、３は純水、５は調合タンクを示す。また６は反
応泥進に用いる電磁波発生器で、７が薬液貯蔵タンクで
ある。フィルタ（図示せず）は１，２．３から調合タン
ク５までの管路に設けられる。FIG. 1 is a diagram explaining the principle of the present invention. In the figure, 1.2 indicates a drug stock solution, 3 indicates pure water, and 5 indicates a mixing tank. Further, 6 is an electromagnetic wave generator used to advance the reaction, and 7 is a chemical storage tank. A filter (not shown) is provided in the pipeline from 1, 2.3 to the mixing tank 5.
本発明では、第１図の調合タンク５内の調合液に電磁波
６を照射することにより、液温を上昇させることなく反
応を短時間に平衡にするものである。電磁波の波長がｌ
ｎｍ未満であると電磁波としてはＸ線となり危険が伴う
からであり、一方４００ｎｍを越えると反応の活性化に
効果がない。In the present invention, by irradiating electromagnetic waves 6 to the liquid mixture in the mixing tank 5 shown in FIG. 1, the reaction is brought to equilibrium in a short time without increasing the temperature of the liquid. The wavelength of electromagnetic waves is l
This is because if the wavelength is less than 400 nm, the electromagnetic waves become X-rays, which is dangerous. On the other hand, if the wavelength exceeds 400 nm, there is no effect on activating the reaction.
又、本発明では従来のように中和滴定などによらないで
、−旦調合された薬液のエッチレートを直接測定し、所
望の濃度が得られるように純水あるいは薬品原液を調合
液に供給する。すなわち、中和滴定などの化学分析は時
間がかかるため使用せず、エッチレートの測定を行なう
。エッチレートを迅速に測定するためには、例えば１分
程度の短時間て除去される皮膜厚みの試料を、例えば２
００〜３００人の範囲内で１０人間隔の厚みの５ｉｎ２
皮膜を有する試料を用意しておき、これらをタンク５内
の薬液に浸漬し、１分後に引上げ、皮膜の有無を目視て
確認すればよい。その後、純水又、薬液原液、あるいは
所定濃度の希釈液等を補充するが、その補充量を定める
ためには、予め薬品２８度とエッチレートの関係を求め
ておき、エッチレート実測値から薬液濃度を算定し、こ
れより不足（過剰）薬液量を、予め求められた関１系に
基づき、計算することが必要である。In addition, in the present invention, the etch rate of the prepared chemical solution is directly measured, and pure water or the drug stock solution is supplied to the mixed solution to obtain the desired concentration, without using neutralization titration as in the conventional method. do. That is, chemical analysis such as neutralization titration is not used because it takes time, but the etch rate is measured. In order to quickly measure the etch rate, a sample with a film thickness that can be removed in a short period of time, e.g. 1 minute, is
5in2 with a thickness of 10 people between 00 and 300 people
Samples having a film may be prepared in advance, immersed in the chemical solution in the tank 5, pulled out after 1 minute, and visually checked for the presence or absence of the film. After that, pure water, undiluted chemical solution, or diluted solution of a predetermined concentration is replenished, but in order to determine the amount of replenishment, the relationship between the chemical 28 degrees Celsius and the etch rate is determined in advance, and the chemical solution is calculated from the actual etch rate value. It is necessary to calculate the concentration, and then calculate the insufficient (excess) amount of the drug solution based on the predetermined Seki 1 system.
続いて、その不足；８度に相当する薬液を補充するか、
あるいは過剰量に相当する純水を補給する。Next, if there is a shortage; replenish the chemical solution equivalent to 8 degrees,
Alternatively, replenish pure water equivalent to the excess amount.
補給量が多いとき、あるいは直ちに調合液をウェットプ
ロセスに供給しなければならないときは調合薬液に再び
電磁波を照射する。When the amount of replenishment is large or when the compounded liquid must be immediately supplied to the wet process, the compounded chemical solution is irradiated with electromagnetic waves again.
［作用］
本発明によれば、電磁波を調合液に照射することにより
エッチレートが短時間に安定するので、かかるエッチレ
ートを調合後、短時間内で直接測定すれば、得られたエ
ッチレートに基づいて任意の濃度のエツチング液を短時
間で調製できる。[Function] According to the present invention, the etch rate is stabilized in a short time by irradiating the prepared solution with electromagnetic waves, so if the etch rate is directly measured within a short time after being prepared, the obtained etch rate can be confirmed. Based on this, an etching solution of any concentration can be prepared in a short time.
以下、実施例により本発明の詳細な説明する。Hereinafter, the present invention will be explained in detail with reference to Examples.
［実施例〕
容量でＮＨ４Ｆ２２％、ＨＦ３．５％からなるエツチン
グ液を調合し、１〜７時間放置後Ｓｉ○２を２０℃でエ
ツチングした時のエツチレ−１−（１分当りのエツチン
グ量）を第２図に示す（○−○）。[Example] An etching solution consisting of 22% NH4F and 3.5% HF by volume was prepared, and after being left for 1 to 7 hours, Si○2 was etched at 20°C. Etch-1- (etching amount per minute) are shown in Figure 2 (○−○).
電磁波を照射しない、この場合のエッチレートは経過時
間とともに僅かづつ増加していることが分かる９
一方、上記方法で調合後、水銀ランプにより紫外線（波
長−３６５ｎｍ）を照射した調合液では、１．５時間経
過後にエッチレート（Ｘ−Ｘ）は安定したレベルに達し
ている。従って、紫外線照射ｔ＆１．５時間が経過した
エッチレートを測定すると、安定したエッチレートを求
めることができる。It can be seen that the etch rate in this case without irradiation with electromagnetic waves increases slightly with elapsed time. After 5 hours, the etch rate (XX) reached a stable level. Therefore, by measuring the etch rate after t&1.5 hours of ultraviolet irradiation, a stable etch rate can be determined.
次に、液量５００ｍρでＮＨ４Ｆ（２３％）を一定にし
て、ＨＦ濃度を変えた溶液に水銀ランプで紫外線を照射
し、その後中和滴定でＨＦ濃度を測定し、またエッチレ
ートを求めた。結果を第３図に示す。Next, with a liquid volume of 500 mρ and a constant NH4F (23%), the solutions with varying HF concentrations were irradiated with ultraviolet light using a mercury lamp, and then the HF concentrations were measured by neutralization titration, and the etch rates were also determined. The results are shown in Figure 3.
第３図と同じ直線を第４図に示す９図中○マークの濃度
のエツチング液を別に用意し、前述と同じように紫外線
照射し、これによりエツチングを行なったところ、三つ
の×マークで示すエッチレートが得られた。したがって
、中和滴定とエッチレート測定ではほぼ同じ結果が得ら
れることが分かる。The same straight line as in Fig. 3 is shown in Fig. 4. An etching solution with the concentration indicated by the ○ mark in Fig. 9 was prepared separately, and the etching solution was irradiated with ultraviolet rays in the same manner as described above. The etch rate was obtained. Therefore, it can be seen that almost the same results are obtained in neutralization titration and etch rate measurement.
［発明の効果］
以上説明した様に、本発明によれば、エッチレートの確
認により、任意の濃度が精度よく設定できるのてエツチ
ング液の自動補給が容易になる。[Effects of the Invention] As described above, according to the present invention, by checking the etch rate, any desired concentration can be set with high precision, thereby facilitating automatic replenishment of the etching solution.
第１図は本発明の原理説明図、
第２図はエッチレートの経時変化を示すグラ乙
第３図は、中和滴定で求められたＨＦ濃度とエッチレー
トの関係を示すグラフ、
第４図は 中和滴定とエッチレート測定の両方の方法で
求められたＨＦ濃度とエッチレートの関係を示すグラフ
である。
１．２−薬品原液、３−純水、５−調合タンク、６−電
磁波発生器
ｑコ
臂
Ｈ＞＋Δ−工 〈Figure 1 is an explanatory diagram of the principle of the present invention. Figure 2 is a graph showing changes in etch rate over time. Figure 3 is a graph showing the relationship between HF concentration and etch rate determined by neutralization titration. Figure 4 is a graph showing the relationship between HF concentration and etch rate determined by both neutralization titration and etch rate measurement methods. 1. 2-Drug stock solution, 3-Pure water, 5-Preparation tank, 6-Electromagnetic wave generator q arm H>+Δ-work
Claims (1)
磁波を照射し、その後前記薬液により被処理物質をエッ
チングしエッチレートを測定し、予め求められた前記薬
液と前記被処理物質のエッチレートの関係に基づいて、
必要により、薬液濃度を所定値に調節することを特徴と
するエッチング液調合方法。1. Irradiate an etching chemical solution with electromagnetic waves with a wavelength of 1 nm to 400 nm, then etch the substance to be treated with the chemical liquid and measure the etch rate, and obtain the predetermined relationship between the etch rate of the chemical liquid and the substance to be treated. based on,
An etching solution preparation method characterized by adjusting the concentration of the chemical solution to a predetermined value as necessary.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29891288A JPH02143525A (en) | 1988-11-25 | 1988-11-25 | Etchant preparation |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP29891288A JPH02143525A (en) | 1988-11-25 | 1988-11-25 | Etchant preparation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH02143525A true JPH02143525A (en) | 1990-06-01 |
Family
ID=17865783
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP29891288A Pending JPH02143525A (en) | 1988-11-25 | 1988-11-25 | Etchant preparation |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH02143525A (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011099089A1 (en) * | 2010-02-15 | 2011-08-18 | パナソニック株式会社 | Method for producing semiconductor device and device for producing semiconductor device using same |
-
1988
- 1988-11-25 JP JP29891288A patent/JPH02143525A/en active Pending
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO2011099089A1 (en) * | 2010-02-15 | 2011-08-18 | パナソニック株式会社 | Method for producing semiconductor device and device for producing semiconductor device using same |
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