TW200305794A - Method for determining the concentration of alkaline developer and method for preparing developer - Google Patents
Method for determining the concentration of alkaline developer and method for preparing developer Download PDFInfo
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- TW200305794A TW200305794A TW92106924A TW92106924A TW200305794A TW 200305794 A TW200305794 A TW 200305794A TW 92106924 A TW92106924 A TW 92106924A TW 92106924 A TW92106924 A TW 92106924A TW 200305794 A TW200305794 A TW 200305794A
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- 238000000034 method Methods 0.000 title claims abstract description 52
- 238000003384 imaging method Methods 0.000 claims description 102
- 238000005259 measurement Methods 0.000 claims description 30
- 239000007788 liquid Substances 0.000 claims description 24
- 238000012360 testing method Methods 0.000 claims description 18
- 238000002059 diagnostic imaging Methods 0.000 claims description 16
- 150000003839 salts Chemical class 0.000 claims description 16
- 239000002253 acid Substances 0.000 claims description 11
- 239000002699 waste material Substances 0.000 claims description 11
- 239000003513 alkali Substances 0.000 claims description 10
- 229910052799 carbon Inorganic materials 0.000 claims description 9
- 230000000694 effects Effects 0.000 claims description 9
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 8
- 230000001568 sexual effect Effects 0.000 claims description 8
- BVKZGUZCCUSVTD-UHFFFAOYSA-N carbonic acid Chemical compound OC(O)=O BVKZGUZCCUSVTD-UHFFFAOYSA-N 0.000 claims description 6
- 238000001514 detection method Methods 0.000 claims description 6
- 238000011084 recovery Methods 0.000 claims description 6
- 230000002378 acidificating effect Effects 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 230000001590 oxidative effect Effects 0.000 claims description 2
- 238000009434 installation Methods 0.000 claims 2
- 206010029412 Nightmare Diseases 0.000 claims 1
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 claims 1
- 101100218353 Talaromyces purpureogenus axeA gene Proteins 0.000 claims 1
- 230000015556 catabolic process Effects 0.000 claims 1
- 230000003749 cleanliness Effects 0.000 claims 1
- 239000010808 liquid waste Substances 0.000 claims 1
- 238000000691 measurement method Methods 0.000 claims 1
- 230000003472 neutralizing effect Effects 0.000 claims 1
- 239000000243 solution Substances 0.000 description 61
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 28
- 238000004448 titration Methods 0.000 description 23
- 229910002092 carbon dioxide Inorganic materials 0.000 description 16
- 150000005323 carbonate salts Chemical class 0.000 description 15
- 238000011161 development Methods 0.000 description 15
- 230000018109 developmental process Effects 0.000 description 15
- 229960004424 carbon dioxide Drugs 0.000 description 14
- 239000001569 carbon dioxide Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 10
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 9
- -1 dimethyl dicholine Chemical compound 0.000 description 9
- 150000002500 ions Chemical class 0.000 description 9
- 238000006386 neutralization reaction Methods 0.000 description 9
- 238000004519 manufacturing process Methods 0.000 description 7
- 238000005516 engineering process Methods 0.000 description 5
- 238000007726 management method Methods 0.000 description 5
- 229920002120 photoresistant polymer Polymers 0.000 description 5
- 239000004065 semiconductor Substances 0.000 description 5
- 239000012085 test solution Substances 0.000 description 5
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- BVKZGUZCCUSVTD-UHFFFAOYSA-M Bicarbonate Chemical compound OC([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-M 0.000 description 4
- 239000000203 mixture Substances 0.000 description 4
- 230000008929 regeneration Effects 0.000 description 4
- 238000011069 regeneration method Methods 0.000 description 4
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 3
- 238000010521 absorption reaction Methods 0.000 description 3
- 125000005588 carbonic acid salt group Chemical group 0.000 description 3
- 239000001257 hydrogen Substances 0.000 description 3
- 229910052739 hydrogen Inorganic materials 0.000 description 3
- 239000004973 liquid crystal related substance Substances 0.000 description 3
- 238000003918 potentiometric titration Methods 0.000 description 3
- 239000000758 substrate Substances 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 2
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Natural products CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 2
- 241001674048 Phthiraptera Species 0.000 description 2
- 235000011114 ammonium hydroxide Nutrition 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
- AYJRCSIUFZENHW-UHFFFAOYSA-L barium carbonate Chemical compound [Ba+2].[O-]C([O-])=O AYJRCSIUFZENHW-UHFFFAOYSA-L 0.000 description 2
- 239000012159 carrier gas Substances 0.000 description 2
- 125000004177 diethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 2
- 238000010790 dilution Methods 0.000 description 2
- 239000012895 dilution Substances 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 239000012458 free base Substances 0.000 description 2
- 150000004679 hydroxides Chemical class 0.000 description 2
- 239000012216 imaging agent Substances 0.000 description 2
- 239000004615 ingredient Substances 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 239000001301 oxygen Substances 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 230000001172 regenerating effect Effects 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- 125000005207 tetraalkylammonium group Chemical group 0.000 description 2
- WGTYBPLFGIVFAS-UHFFFAOYSA-M tetramethylammonium hydroxide Chemical compound [OH-].C[N+](C)(C)C WGTYBPLFGIVFAS-UHFFFAOYSA-M 0.000 description 2
- RYHBNJHYFVUHQT-UHFFFAOYSA-N 1,4-Dioxane Chemical compound C1COCCO1 RYHBNJHYFVUHQT-UHFFFAOYSA-N 0.000 description 1
- 125000000954 2-hydroxyethyl group Chemical group [H]C([*])([H])C([H])([H])O[H] 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- GAWIXWVDTYZWAW-UHFFFAOYSA-N C[CH]O Chemical group C[CH]O GAWIXWVDTYZWAW-UHFFFAOYSA-N 0.000 description 1
- 206010011469 Crying Diseases 0.000 description 1
- 206010034972 Photosensitivity reaction Diseases 0.000 description 1
- 239000007983 Tris buffer Substances 0.000 description 1
- 150000008043 acidic salts Chemical class 0.000 description 1
- 125000005210 alkyl ammonium group Chemical group 0.000 description 1
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 1
- 239000000908 ammonium hydroxide Substances 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 description 1
- 150000004649 carbonic acid derivatives Chemical class 0.000 description 1
- 150000001767 cationic compounds Chemical class 0.000 description 1
- 150000001768 cations Chemical group 0.000 description 1
- 239000003610 charcoal Substances 0.000 description 1
- 150000001793 charged compounds Chemical class 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000470 constituent Substances 0.000 description 1
- 238000012937 correction Methods 0.000 description 1
- 239000013078 crystal Substances 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000007865 diluting Methods 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 238000004945 emulsification Methods 0.000 description 1
- 125000001495 ethyl group Chemical group [H]C([H])([H])C([H])([H])* 0.000 description 1
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 description 1
- 125000003983 fluorenyl group Chemical group C1(=CC=CC=2C3=CC=CC=C3CC12)* 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000002309 gasification Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 150000007857 hydrazones Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000011261 inert gas Substances 0.000 description 1
- 150000007529 inorganic bases Chemical class 0.000 description 1
- 229910052806 inorganic carbonate Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 230000010354 integration Effects 0.000 description 1
- 230000000873 masking effect Effects 0.000 description 1
- 238000004377 microelectronic Methods 0.000 description 1
- 230000007935 neutral effect Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- XEBWQGVWTUSTLN-UHFFFAOYSA-M phenylmercury acetate Chemical compound CC(=O)O[Hg]C1=CC=CC=C1 XEBWQGVWTUSTLN-UHFFFAOYSA-M 0.000 description 1
- 230000036211 photosensitivity Effects 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000012492 regenerant Substances 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 230000000284 resting effect Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000012488 sample solution Substances 0.000 description 1
- STECJAGHUSJQJN-FWXGHANASA-N scopolamine Chemical class C1([C@@H](CO)C(=O)O[C@H]2C[C@@H]3N([C@H](C2)[C@@H]2[C@H]3O2)C)=CC=CC=C1 STECJAGHUSJQJN-FWXGHANASA-N 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002689 soil Substances 0.000 description 1
- 238000009331 sowing Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000009182 swimming Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- CBXCPBUEXACCNR-UHFFFAOYSA-N tetraethylammonium Chemical compound CC[N+](CC)(CC)CC CBXCPBUEXACCNR-UHFFFAOYSA-N 0.000 description 1
- LPSKDVINWQNWFE-UHFFFAOYSA-M tetrapropylazanium;hydroxide Chemical compound [OH-].CCC[N+](CCC)(CCC)CCC LPSKDVINWQNWFE-UHFFFAOYSA-M 0.000 description 1
- 239000010409 thin film Substances 0.000 description 1
- 235000012431 wafers Nutrition 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3504—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light for analysing gases, e.g. multi-gas analysis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
- G01N31/162—Determining the equivalent point by means of a discontinuity
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N31/00—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods
- G01N31/16—Investigating or analysing non-biological materials by the use of the chemical methods specified in the subgroup; Apparatus specially adapted for such methods using titration
- G01N31/162—Determining the equivalent point by means of a discontinuity
- G01N31/164—Determining the equivalent point by means of a discontinuity by electrical or electrochemical means
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Molecular Biology (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Photosensitive Polymer And Photoresist Processing (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Exposure Of Semiconductors, Excluding Electron Or Ion Beam Exposure (AREA)
Abstract
Description
200305794 五、發明說明（1) 發明所屬之技術領域： m係有關於半導體器件 板專的電子元件等製裎方面所 貝丁的P刷冤峪 像液、該顯像廢液戋哕A & 的光致抗蝕劑用鹼性顯 收或再生方^ 的濃度測定、濃度管理、回 先前技術…度測定裝置等。 在半導體器件、液曰顧千突 件等製程方面，一般係；：微;;制::刷電路板等的電子元 晶圓或玻璃基板等的基 ^ ^釦。试影製程係藉由在 掩蔽圖樣等，在Α叫a y成光致抗蝕劑的薄膜，使用 形成精細的圖樣：牛二部分照射光等，以顯像液來顯像而 光部分對於顯ίSiΪ °此處光致抗钱劑類大致區分為曝 曝光部分對於溶的正型光致抗餘劑' …反地 器件或液晶顯;員不可溶的負型光致抗餘劑。半導體 光致抗蝕劑，作二:的電子元件的製造領域主要使用正型 性顯像液。並且’、，、° Λ正型光致抗蝕劑用的顯像液係使用鹼 像液的情形。 卩使是負型光致抗蝕劑也有使用鹼性顯 作為驗性&作 有機鹼的任一稽垛液的鹼性顯像成分，雖可使用無機鹼、 的電子元件之製户J於上述半導體：？晶、印刷電路板等 機鹼之鹼性顯^f，通常係採用虱虱化四烷基銨等的有 並且，鹼夜來加以使用。 碳，則構成上^ 2像液若經由與空氣相接觸而溶入二氣化 係該平衡離子=二性顯像成分之羥離子被消耗#，例如， 叩驗性陽離子形成碳酸氫鹽或碳酸趟200305794 V. Description of the invention (1) The technical field to which the invention belongs: m is a P-paste image liquid, which is used in the manufacture of electronic components such as semiconductor device boards, and the development waste liquid A & The photoresist is used for alkaline concentration measurement or regeneration, concentration measurement, concentration management, back to the prior art ... degree measurement device, etc. In terms of manufacturing processes for semiconductor devices, liquid components, and other components, the general system is: microelectronics; manufacturing: electronic components such as circuit boards or wafers or substrates such as glass substrates. The audition process is to form a thin film of photoresist by masking the pattern in A, etc., and use it to form a fine pattern: the two parts of the cow are irradiated with light, etc., and the image is developed with a developing solution. ° The photoinhibitors here are roughly divided into positive photoresistants that are soluble in the exposed part of the photoresistor's anti-ground device or liquid crystal display; negative photoinhibitors that are insoluble. Semiconductor photoresists are mainly used in the manufacturing of electronic components in the field of electronic components. In addition, when the developing solution for the positive photoresist is an alkali imaging solution. Even if it is a negative photoresist, it also has an alkaline imaging component that uses an alkaline display as a test & organic liquid. Although it is possible to use an inorganic base, the manufacturer of electronic components The above semiconductors:? Crystals, printed circuit boards, and other organic alkalinity are generally used, such as tetraalkylammonium lice, and alkali. Carbon, if the ^ 2 image solution is dissolved into the two-gasification system by contacting with air, the counter ion = the hydroxyl ion of the amphoteric imaging component is consumed #, for example, the test cation forms bicarbonate or carbonate trip
200305794 五、發明說明（2) 下，亦稱為 性陽離子形 化物的狀態 的溶入而生 液於供給至 類。並且， 溶解起來， 近年來 由加工精確 像步驟所使 定且有效地 於半導 若使用鹼性 像效果。因 0. 0 0 2 t * °/〇 通常， 液、以及再 性成分係， 差滴定裝置 測定。特別 測，故受到 發明内容： 發明所欲解 然而， 碳酸系鹽類）。 成平衡離子，在 )而具有顯像活 成碳酸系鹽類， 半導體製程的時 由於鹼性顯像液 而有碳酸系鹽類 ^ LS I ^LCD Pit t 度與生產效率的 用的光致抗蝕劑 顯像之要求逐漸 體器件或液晶裝 顯像成分為2 . 3 8 此5可嘗試南精 左右的範圍内來 於顯像步驟所供 生驗性顯像液中 於該濃度調製步 、導電率計、超 是導電率計和超 廣泛使用。 鹼性顯像成分係，羥離子與鹼 顯像液中以游離的狀態（氫氧 性。因此，經由基於二氧化碳 以致顯像活性減低。驗性顯像 候，多已含有少量的碳酸系鹽 經反覆使用，二氧化碳緩緩地 的濃度逐漸增加的趨勢。 精細化、高集成化不斷進展， 觀點看來，對於正確地控制顯 的顯像液濃度，使精細圖樣穩 昇高起來。 置等製程所使用的顯像液可知 重量％的濃度則具最有效的顯 確度地稀釋調整至此濃度的土 加以使用。 給的鹼性顯像液、鹼性顯像廢 的顯像成分，例如T A A Η等的驗 驟中，藉由ρ Η滴定裝置、電位 音波濃度計等的測定裝置加以 音波濃度計，由於適合連續計 決的課題： 即使使用高性能的濃度測定裝置，對於鹼性顯200305794 V. Description of the invention (2), also known as the state of sexual cationic compounds, the liquid is supplied to the class. In addition, it dissolves, and in recent years, it is determined by the processing of precise imaging steps and is effective for semiconducting if an alkaline imaging effect is used. Because of 0.02 t * ° / 〇 Usually, liquid and regenerant components are measured by a differential titration device. Specially tested, it is subject to the invention. Contents of the invention: However, carbonate salts). It is a counter ion, and it has imaging active carbonic acid salts. In the semiconductor manufacturing process, there are carbonic acid salts due to the alkaline imaging solution. ^ LS I ^ LCD Pit t Photosensitivity and production efficiency The requirement for the development of the etch is that the device or the liquid crystal device has a developing component of 2. 3 8 This 5 can be tried in the range of Nanjing from the concentration in the testing solution provided in the developing step at the concentration modulation step, Conductivity meters, ultra-conductivity meters and ultra-widely used. Basic imaging component system, hydroxyl ion and alkaline imaging solution are in a free state (hydroxide. Therefore, the development activity is reduced by carbon dioxide. As a result of diagnostic imaging, most of them already contain a small amount of carbonate salts. Repeated use, the concentration of carbon dioxide gradually increases. Refinement and high integration continue to progress. From a viewpoint, for the correct control of the concentration of the developing solution, the fine pattern steadily rises. The imaging solution used shows that the concentration of wt% is the most effective for diluting the soil adjusted to this concentration for use. The alkaline imaging solution and the imaging development waste of alkaline imaging waste, such as TAA Η In the test, a sound densitometer is added to a measuring device such as a ρ Η titration device and a potentiometric sound concentration meter, which is suitable for continuous determination. Even if a high-performance concentration measuring device is used,
2042-5562-PF(Nl) ptd 第7頁 200305794 五、發明說明（3) 像液的濃度控制，實際上卻有所困難。 亦即，對於含有碳酸系鹽類的鹼性顯像液，藉由滴定 ί來測定全部顯像成分濃度，基於該濃度，若對用於濃度 官理的導電率計或超音波濃度計加以校正，則於顯像步驟 中比起作為目的的濃度，有供給較低濃度的氫氧化物濃度 的驗性顯像液之傾向。 並且， (氫氧化物 果，利用此 化物濃度來 藉由煩雜的 )濃度，而 導電率來控 顯像之傾向 滴定技巧以 基於該濃度 制步驟的結 測定游離的 來校正導電 果，則有以 顯像成分 率計，其結 較南的氮氧2042-5562-PF (Nl) ptd Page 7 200305794 V. Description of the invention (3) The concentration control of the image liquid is actually difficult. That is to say, the concentration of all the imaging components is measured by titration of the alkaline imaging solution containing carbonate salts, and based on the concentration, the conductivity meter or ultrasonic densitometer used for concentration management is calibrated. Then, in the developing step, there is a tendency that a test solution with a lower concentration of hydroxide concentration is supplied than the concentration intended. In addition, (hydroxide fruit, the concentration of this compound is used to troubleshoot) the concentration, and the conductivity is controlled by the tendency of the development. Titration techniques to correct the conductive fruit based on the measurement of the freeness based on the results of the concentration step, Imaging composition ratio meter, its nitrogen and oxygen
因此’本發明的目的在於正確地控制含有鹼性顯像成 分之顯像液的濃度，並提供一種用以達成正確而有效的顯 k步驟之顯像液的遭度測定技術。又一目的在於提供一種 含有驗性顯像成分之顯像液的濃度管理、回收或再生技 術。 用以解決課題的手段： 諸位本發明者對於鹼性顯像液的濃度控制之困難性嘗 3式加ΙίΛ研^寸。Therefore, an object of the present invention is to accurately control the concentration of a developing solution containing an alkaline developing component, and to provide a technique for measuring the exposure degree of a developing solution for achieving a correct and effective developing step. Still another object is to provide a technique for managing, recovering or regenerating a concentration of a developing solution containing a diagnostic developing component. Means to solve the problem: The inventors of the present invention have difficulty in controlling the concentration of the alkaline developing solution.
其結果，於鹼性顯像液的濃度測定方面，以往對於碳 酸系鹽類的存在，在容許範圍内，雖被認為沒有計測上的 問題，但藉由此次所採用的技術，才意外地發現這些碳酸 系鹽類對於具有顯像活性的游離鹼性顯像成分之正確的濃 度測定有很大的妨礙這—點。 亦即，可知鹼性顯像液的濃度控制之困難性的原因在As a result, in the measurement of the concentration of the alkaline imaging solution, the existence of carbonate salts has conventionally been considered to have no measurement problems within the allowable range. However, the technology adopted this time unexpectedly It was found that these carbonate salts are a great obstacle to accurate measurement of the concentration of free alkaline imaging components having imaging activity. That is, it can be seen that the reason for the difficulty in controlling the concentration of the alkaline developing solution lies in
2042-5562-PF(Nl) ptd 第8頁2042-5562-PF (Nl) ptd Page 8
200305794 五、發明說明（4) 於··驗性顯像液於取得的時候，一部分鹼性顯像成分已經 變成石反酸系鹽類之點；以及基於使用的過裎中碳酸系鹽類 增加之點；甚至對包含這些碳酸系鹽類的全部顯像成分濃 度加以測定作為有效的顯像成分濃度之點。 因此’在提供至顯像步驟的顯像液之濃度調整步 回收步驟（包含濃縮步驟）、再生步驟（稀釋步^ f I—、 各種步驟，對於測定顯像液中的氫氧化物等二=寺的 为》辰度以及其技巧加以研討的結果發現，藉由測a ’、心成 驗液中的全部顯像成分濃度，同時測定碳酸系蹿^ f種檢 則可排除碳酸系鹽類的影響，能夠正確地測定^ ^ =度， 成分濃度。基於此，而發現得以解決上述的課了 6，像 發明。 凡成本 亦即，本發明提供以下的方法。 ^ )係種含有^〖生^像成分之顯像液之濃度 ;法具有測定顯像液中的游離驗性顯像成分漠度之步驟的 (2 )係一種含有驗性顯像忐八 法，具有測定顯像液中的全部77 &之顯像液之濃度測定方 驟、以及測定顯像液中的^ :性顯像成分的濃度之步 法。 灭s义糸鹽類的濃度之步驟的方 (3 )如（2 )項所述的方法， 位差滴定裝置、導電率測定筆；中使用中和，定震置、電 超音波傳播速度測定裝置之^ 、相位差測疋裝置、以及 部鹼性顯像成分濃度。 的任-種裝置來測定前述全200305794 V. Description of the invention (4) At the time when the diagnostic imaging solution was obtained, a part of the alkaline imaging components had turned into litho-acid salts; and based on the increase in carbonate salts used in the process Point; even the concentration of all the imaging components containing these carbonate salts is measured as the effective imaging component concentration. Therefore, the concentration adjustment step of the developing solution provided to the developing step includes a recovery step (including a concentration step), a regeneration step (a dilution step ^ f I—, various steps, and the like for measuring the hydroxide in the developing solution. As a result of the research on "Chen Du" and its techniques, it was found that by measuring the concentration of all the imaging components in a 'and Xincheng test solution, and simultaneously measuring the carbonic acid ^^ f test, the carbonate salts can be excluded. Influence, can accurately measure the degree of ^ ^ = degree, the concentration of ingredients. Based on this, it was found that the above lesson 6 was solved, like invention. Where the cost is, the present invention provides the following methods. ^) Department contains ^ 〖生^ The concentration of the imaging solution in the imaging solution; the method (2) having a step of measuring the insensitivity of the free diagnostic imaging component in the imaging solution is a method containing diagnostic imaging. All 77 & concentration measuring steps of the measuring solution and the step method for measuring the concentration of the sexual developing component in the developing solution. (3) The method described in item (2) of the step of destroying the concentration of scopolamine salts, a parametric titration device, and a conductivity measuring pen; neutralization, stationary vibration setting, and electric ultrasonic wave velocity measurement Device ^, phase difference measurement device, and partial alkaline imaging component concentration. Any kind of device to determine the foregoing
200305794 用二氧化碳 五、發明說明（5) (4 )如（2 )或（3 )項所述的方法，其中使 測定裝置來測定前述碳酸系發類濃度。 、…并£ (5 )如（4 )項所述的方法，其中前述二氧化被’則疋衣 包含紅外線二氧化碳檢測裝置° ( 5 )項 (6 ) —種顯像液的調製方法’具有實施如（1 ) 之中任 (7 )- -項所述的顯像液之浪度測定方法的步驟 （5 ) 種顯像廢液的回收方法，具有實施如（1 )〜 項之中任一項所述的顯像液之濃度測定方法的步驟（5 ) (8 ) —種顯像廢液的再生方法’具有貫批如（1 ) 項之中任一項所述的顯像液之濃度測定方法的步」驟方 (9 )係一種含有鹼性顯像成分之顯像液的浪度官理、八濃 法，將游離的鹼性顯像成分濃度作為有效驗性顯像成刀 度的方法。 ^ ^ (1 0 )係一種含有鹼性顯像成分之顯像液的濃度官理八 法，使用基於以下第（1 )式所求得的有效驗性顯像刀 濃度以對顯像液進行濃度管理的方法。 上# 、、曲存一構成板 有效驗性顯像成分濃度=全部驗性顯像成欠）辰展 、 酸系鹽類之鹼性顯像成分濃度· · · · ·第（1 )式十 (11 )係一種含有驗性顯像成分之顯像液的濃度别i ^、 置，具有測定顯像液中的游離鹼性顯像成分濃度之裝、及 或測定顯像液中的全部鹼性顯像成分的濃度之裝置 以 測定顯像液中的碳酸系鹽類的濃度之裝置。 (1 2 )係一種含有鹼性顯像成分之顯像廢液的再生表f、則 具有測定顯像液中的游離鹼性顯像成分濃度之裝置、或u200305794 Using carbon dioxide 5. Description of the invention (5) (4) The method according to item (2) or (3), wherein a measuring device is used to measure the concentration of the aforementioned carbonic acid-based hair. (5) The method according to item (4), wherein the above-mentioned dioxide is 'Then the garment contains an infrared carbon dioxide detection device ° (5) Item (6) — A method for preparing a developing solution' has an implementation Step (5) of the method for measuring the degree of fluctuation of a developing solution according to any one of (1) to (1), (5) A method for recovering developing waste liquid, having the implementation of any one of (1) to (1) to Step (5) (8) of a method for measuring the concentration of a developing solution according to the item (5) (8)-A method for regenerating a developing waste liquid having a concentration of the developing solution according to any one of the items (1) The step of the method of measurement "(9) is a longitude method and eight concentration method of a developing solution containing an alkaline imaging component. The concentration of the free alkaline imaging component is used as an effective diagnostic imaging tool to obtain a knife degree. Methods. ^ ^ (1 0) is an eight-element concentration method of a developer containing an alkaline developer. The effective test developer concentration obtained based on the following formula (1) is used to perform the developer solution. Methods for concentration management. Upper #, Qucun, a composition plate effective diagnostic imaging component concentration = all diagnostic imaging components are insufficient) Chen Zhan, the concentration of alkaline imaging components of acid salts · · · · · (10) Formula 10 (11) It is a concentration solution of a developing solution containing a diagnostic imaging component, and has a device for measuring the concentration of a free alkaline developing component in the developing solution, and / or measuring all the alkali in the developing solution. The device for measuring the concentration of sexual imaging components is a device for measuring the concentration of carbonate salts in a developing solution. (1 2) is a regeneration table f of a developing waste liquid containing an alkaline developing component, and has a device for measuring the concentration of the free alkaline developing component in the developing solution, or u
2042-5562-PF(Nl) ptd 第10頁 200305794 五、發明說明（6) 定顯像液中的 顯像液中的碳 若依據這 部顯像成分濃 製包含著可發 顯像步驟中能 為能夠實施正 並且，若 度、或全部顯 含有鹼性顯像 貫施方式· 以下，就 有關本發 技術在於測定 定顯像液中的 酸系鹽類的濃 又藉由使 及濃度測定裝 或調製、顯像 (鹼性顯 驗性顯像 的有機驗，雖 (TAAH )較佳 (TMAH )、氫 本發明的實施 明的含有驗性 顯像液中的游 全部鹼性顯像 度。 用此項濃度測 置，而能夠達 廢液的回收或 像成分） 成分若為在製 未特別加以限 °作為TAAH， 氧化四乙基銨 度之裝置、以及測定 全部鹼性顯 酸系鹽類的 些發明，藉 度與碳酸系 揮顯像活性 夠供給正確 確而有效的 基於這些發 像成分濃度 成分之顯像 像成分的濃 濃度之裝置 由測定游離 鹽類濃度， 的顯像成分 控制濃度的 顯像步驟。 明，藉由測 與碳酸系鹽 液所具有的 方式作詳 顯像成分 離驗性顯 成分的濃 定技術、 成顯像液 再生技術 造各種電 定，但最 例如可舉 、氫氧化 顯像成分濃 則能夠既定 之顯像液。 鹼性顯像液 定游離顯像 類濃度，則 顯像活性。 細的說明。 之顯像液的 像成分濃度 度以及顯像 亦即濃度測 的濃度調整 子元件等之 好是氫氧化 出：氫氧化 四丙基銨、 度、或全 濃度地調 因此，在 。此結果 成分濃 能夠檢測 濃度測定 、或是測 液中的碳 定方法以 (稀釋） 際所使用 四烷基銨 四曱基銨 氫氧化四2042-5562-PF (Nl) ptd Page 10 200305794 V. Description of the invention (6) The carbon in the developing solution of the fixed developing solution, if concentrated according to this developing component, contains the energy that can be developed in the developing step. In order to be able to implement positive and alkaline development, if all or all of them contain alkaline imaging, the following technology will be used to measure the concentration of acid salts in a fixed imaging solution. Or it can be prepared and developed (organic test for alkaline diagnostic imaging, although (TAAH) is better (TMAH), hydrogen) The embodiment of the present invention contains all the alkaline imaging in the diagnostic imaging solution. With this concentration measurement, the recovery of waste liquid or image components can be achieved.) If the components are not specifically limited in production, it is used as a TAAH, a device for oxidizing tetraethylammonium, and measuring all basic acidic salts. Some of the inventions are capable of supplying accurate and effective devices based on the concentration of the imaging components based on the concentration of these imaging components, and the concentration of the imaging components to determine the concentration of the imaging components by measuring the concentration of free salts. Development steps. It is clear that the concentration determination technology that separates the sensible development components and the development technology of the development solution to make various types of electrical measurements by measuring the method of the carbonated salt solution. Concentrated ingredients can be used as the developer. When the alkaline imaging solution is used to determine the concentration of free imaging agents, the imaging activity is obtained. Detailed instructions. The concentration of the imaging component of the imaging solution and the concentration adjusting sub-elements of the imaging, that is, the concentration measurement, are preferably hydroxides: tetrapropylammonium hydroxide, degrees, or full concentration. Therefore, in. This result can be used to measure the concentration of the component, or to determine the concentration of carbon in the solution. (Dilute) The tetraalkylammonium tetramethylammonium hydroxide used
2042-5562-PF(Nl) ptd 第11頁 200305794 五、發明說明（7) 丁基銨、氫氧 氧化二甲基二 膽鹼）、氮氧 (2 -羥乙基） 化曱基 敍、氫 烧基錢 這 衡離子 物或游 方面， 鹽的狀 性。然 導電率 於 離的狀 物所包 於顯像 具有顯 係由游 之驗性 全部鹼 特 驟、再 三（2 -氧化四 和氫氧 些驗性 ，幾乎 離狀態 對於製 態，同 而，即 ，並且 本說明 態包含 含的鹼 液中可 像活性 離驗性 顯像成 十生顯像 別是在 生使用 化甲基 乙基1$ 化三乙 錄、氣 羥乙基 (2〜羥 <匕四乙 顯像成 以游離 係驗十生 造如石炭 時消耗 使是該 也有助 書中， 於顯像 性顯像 與輕離 的成分 顯像成 分（典 成分的 稀釋顯 顯像廢 三乙基銨、 、氫氧化三 基（2 -羥乙 氧化二乙基 )敍、氯氧 乙基）銨等 基烧基銨較 分係氫氧化 的狀態包含 顯像成分具 酸根離子或 羥離子，而 鹽，也會在 於超音波傳 所謂游離的 液中的驗性 成分。所謂 子和其他陰 之謂。具體 分、以及和 型者為碳酸 量係這些驗 像原液以調 液之前的稀 氫氧化 曱基（: 基）錢 二（2〜輕 化乙基三 。特別是 佳。 物，亦即 於顯像液 有顯像活 碳酸氫根 無法發揮 中和滴定 播速度等 驗性顯像 顯像成分 全部驗性 離子成對 而言，全 羥離子以 系鹽類的 性顯像成 製既定濃 釋等的濃 曱基乙基錢、氮 羥乙基）銨（即 氫氧化二甲基二 乙基）銨、氫氧 (2 -經乙基） ，氫氧化四甲基 形成經離子與不 中。這種氫氧化 性的狀態。另一 離子般的弱酸與 本來的顯像活 產生反應，具有 成分係 或是作 顯像成 ，於游 部鹼性 外的陰 形態） 分的總 度的顯 度調整 指，以游 為氲氧化 分係指， 離的狀悲 顯像成分 離子成對 所構成。 和 〇 像液之歩 步驟方2042-5562-PF (Nl) ptd Page 11 200305794 V. Description of the invention (7) Butyl ammonium, oxyhydroxide dimethyl dicholine), nitrogen (2-hydroxyethyl) hydrazone, hydrogen Burning base money this counter ion or swimming aspect, the shape of salt. However, the electrical conductivity of the ion-contained object is obviously dependent on the basic properties of the test, and it is repeated (2-oxide and hydrogen). In addition, in this description, the lye-containing solution can be visually separated into a ten-day developmental image. In particular, the use of methyl ethyl 1 $, triethyl ether, and hydroxyethyl (2 ~ hydroxy < The development of Diaosiyi is based on the free system, which can be used to test the lifetime of the product, such as charcoal. It is also helpful in the book. In the developmental imaging and lightly separated components, the imaging components (the dilution of the typical components of the imaging imaging waste three Ethyl ammonium, tris (2-hydroxyethoxylated diethyl) hydroxide, chlorooxyethyl) ammonium, and other basic alkyl ammonium hydroxides include acidic or hydroxyl ions in the imaging component. The salt also lies in the ultrasonic constituents of the so-called free liquid in the so-called free liquid. The so-called sub and other yin are called. The specific points and the type are carbonic acid. These test liquids are diluted with hydroxide before the liquid is adjusted. Fluorenyl (: yl) Qian II (2 ~ lightening ethyl III. Special It is a good substance, that is, in the developing solution, the active bicarbonate cannot be developed to neutralize the titration sowing speed and other diagnostic imaging components. All the diagnostic ions are paired. For all hydroxyl ions, they are salts. Sexual imaging can be used to produce concentrated fluorenyl ethyl acetate, nitroethyl) ammonium (ie, dimethyl diethyl hydroxide), ammonium hydroxide (2-ethyl), and tetramethyl hydroxide. The base forms ions and is not neutral. This hydroxide state. Another ion-like weak acid reacts with the original imaging activity, has a composition system or is developed, and is in the form of an overcast part outside the alkalinity. ） The total degree of brightness adjustment refers to the oxidization of oxygen, which refers to the separation of the image components of the sorrowful imaging components in pairs.
IMIM
2042-5562-PF(Nl) ptd 第12頁 ZUUJU^/V4 五、發明說明（8) 子 峻0¾:虱很離子*以外能存在的主要負離子係奴酸根離子和 的量能夠以、^等的碳酸系離子。因而，全部鹼性顯像成分 顯像成分的畴離鹼性顯像成分、與構成碳酸系鹽類之鹼性 •(游離Ϊ和來加以求得。 直接、、01々岭性顯像成分） 曰 ’、定游離的鹼性顯像成分的濃度是有所困難 面，除了羥離 碳酸氫根離 ^ 1 ，ti、J贩Ί工—…卜 分與《 : ”顯像成分可藉由各別測定全部鹼性顯像成 士乂二％糸鹽類的濃度而得到。此種情形，全部鹼性顯像 成刀的礙度可 ）滴定裝置、電位差滴定 裝置、導番*彳用例如ρ η、 η Μ立、士、曲— ^ 率言十、相位盖濃度計 度計等 士種2 =剛定裝置加以測定。係絕對的定量法，一般而 5 ，由確立作為試驗方法之點、以及精確度之點觀之’則 使用pH (中和）滴定、電位差滴定等的滴定裝置為較佳。 以往’全部驗^顒像成分以及游離的驗性顯像成分係 利用中和滴定以同時求得。亦即，利用一般的中和滴定， 對於全部鹼性顯像^分；又添加氯化鋇而形成碳酸鋇以去 除％I酸系離子，' 分離的驗性顯像成分，以鹽酸各別加 以滴定而能夠定量：" 此全部鹼性顯像成分以及游離驗性顯像成分的滴定係 可以同一溶液連續滴定、亦可以個別溶液分別滴定。 然而，於此^法中，空氣中的二氧化碳在滴定操作中 會與鹼性顯像成分相結合，游離鹼性成分濃度有比實際更 低的趨勢，對於嚴密的測定是：：t視的。 b 因此，本發明為了具有更南精確度的定量，全部鹼性2042-5562-PF (Nl) ptd Page 12 ZUUJU ^ / V4 V. Description of the invention (8) Zijun 0¾: The major negative ions that can exist other than lice are ions * The amount of anoate ions and Carbonic acid ion. Therefore, all of the basic imaging components are separated from the basic imaging components and the alkalinity that constitutes the carbonate salts. (Free sum is calculated. Direct, 01 ridge imaging components) It is difficult to determine the concentration of free alkaline imaging components. In addition to hydroxy ion bicarbonate ionization, ^, Ί, Ί 工 Ί —... Bufen and ":" imaging components can be determined by each Do not measure the concentration of all alkaline imaging agents to obtain a salt concentration of 2% 糸. In this case, the interference of all alkaline imaging tools is acceptable) Titration devices, potentiometric titration devices, and guides. For example, ρ η, η Μ 立, 士, 曲 — ^ Introduction to ten, such as phase cover concentration meter, etc. 2 = Rigid device for measurement. It is an absolute quantitative method, generally 5 and it is established as the point of test method, As for the point of view of accuracy, a titration device using pH (neutralization) titration, potentiometric titration, etc. is preferred. In the past, all the imaging components and free diagnostic imaging components used neutralization titration to simultaneously Calculated. That is, for all basicity using general neutralization titration Addition of barium chloride to form barium carbonate to remove% I acidic ions, 'The separated diagnostic imaging components can be quantified by titration with hydrochloric acid respectively: " All of the alkaline imaging components and The titration system of the free diagnostic imaging component can be continuously titrated in the same solution, or it can be titrated separately for each solution. However, in this method, carbon dioxide in the air will be combined with the alkaline imaging component during the titration operation, and the free base The concentration of sexual components tends to be lower than actual, and for strict measurement is: t depending. B Therefore, in order to quantify with more southern precision, the present invention is all alkaline.
2042-5562-PF(Nl) ptd 200305794 五、發明說明（9) 顯像成分多 碳的影響（ 二氧化碳的 得碳酸成分 碳酸鹽成分 前的問題。 差、指示劑 酸鹽的當量 並且， 用導電率計 率計、相位 於經由其他 測定的游離 碳酸系鹽類 正有必要加 部鹼性顯像 波濃度計所 使計測數據 與碳酸系鹽 若依據 像成分或游 率，碳酸系 敏度的大約 鹼性顯像成2042-5562-PF (Nl) ptd 200305794 V. Description of the invention (9) The effect of multi-carbon of the imaging component (problem of carbon dioxide and carbonate before carbonic acid. Poor, equivalent of indicator acid salt, and conductivity The meter and the phase are located through other measured free carbonate salts. It is necessary to add an alkaline imaging wave concentration meter to make the measured data and carbonate salts based on the image composition or mobility. Sexual imaging
以滴定法等來求得，藉由不受空氣中的二 或不易受影響)之裳置、或是在不受空 匕 影響（或不易文影響）之狀態下的測定，來 的，度，由全部鹼性顯像成分扣除另外求得的 的濃度而求得游離鹼性成分，由此得以解決先 再者’對於滴定終點的決定，雖有pH、電位 專彳旦本發明使用以電位差滴定來決定到達碳 點之終點的方法為較佳。 人 由容易在管線上連續計測的觀點看來，亦可使 、起音波濃度计以及相位差濃度計。使用導電 差濃度計、超音波濃度計等的測定裝置時，基 的中和滴定、電位差滴定等的濃度測定裝置所 鹼性顯像成分的標準溶液之校正、與基於作為 的鹼性顯像成分的標準溶液之校正，對此種校 以施行。藉由這種校正，至少在所欲控制的全It can be obtained by titration, etc., by measuring the degree of freedom from being placed in the air, or in a state that is not affected by air daggers (or not easily affected by text), The free alkaline component is obtained by subtracting the separately obtained concentration from all the basic imaging components, so that the determination of the end point of the titration can be solved. Although there are pH and potential, the present invention uses titration by potential difference. The method to determine the end point of the carbon point is preferred. From the standpoint of easy continuous measurement on the pipeline, it is also possible to use an acoustic wave density meter and a phase difference density meter. When using a measuring device such as a conductivity difference densitometer and an ultrasonic densitometer, the calibration of the standard solution of the basic developing component in the concentration measuring device such as neutralization titration and potentiometric titration, and the basic developing component based on the The calibration of the standard solution is implemented for this kind of calibration. With this correction, at least
計測的 對應於 类員的鹼 諸位本 離鹼性 襲類具 〜半的 >與濃 濃度範圍内，確定基於導電率計或超4 數據、與各別濃度之間的關係，則能多 全部鹼性顯像成分（游離鹼性顯像成$ 性顯像成分之和）的濃度。 發明者則可知，例如有關於全部鹼性蔡 顯像成分濃度為2 · 3 8重量％附近的導ί 有游離驗性顯像成分所具有的導電率1 靈敏度。亦即，可知含有濃度A的游離 度B的碳酸系鹽類鹼性顯像成分的情The measured alkalis corresponding to the class members are about ½ of the basic attack class and the concentration range, and the relationship between the concentration and the concentration based on the conductivity meter or super 4 data can be determined. Concentration of alkaline imaging components (the sum of free alkaline imaging components and sex imaging components). The inventors knew, for example, that the conductivity of the free diagnostic imaging component has a sensitivity of about 1 to 38% by weight in the case where the concentration of all the basic Cai imaging components is around 2.38% by weight. In other words, it can be seen that the carbonate-based alkaline imaging components containing the freeness B at the concentration A
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200305794200305794
形，導 另 氣中的 不受空 來測定 易受影 或是二 間短、 點的顯 定裝置 市售的 等較佳 以及以 co: 產生槽 空氣等 空空間 電率係與濃度A及濃度〇· 5B的和成比例。 -方面，碳酸系鹽類的濃度係，如上述， 二氧化石反的影響（或不易受影響） 影響（或不易受影響 為較佳。作為不文空氣中的二氧化碳的 響）之裝置，可舉出直接測定顯 ：: 氧化碳量的方法。—般而言，由：：無機妷里 ΐΓ 能夠正確地測定在測定時 仏液中的一乳化妷量。作為無機碳或二氧化碳的測 ，雖可採用各種先前的裝置，彳θ # 'It is better to measure the susceptibility to shadows or two short and spot display devices that are not commercially available in the shape of the air. It is better to use the co: generating tank air and other empty spaces. The sum of 5B is proportional. -In terms of the concentration of carbonic acid salts, as mentioned above, the device (or less susceptible to the impact) of the impact of the dioxide (or less susceptible is better. As a device of carbon dioxide in the air), it can be Give a method to directly determine the amount of carbon dioxide :. In general, from :: inorganic 妷 妷 Γ can accurately measure the amount of an emulsified 妷 in the 仏 solution during the measurement. For the measurement of inorganic carbon or carbon dioxide, although various previous devices can be used, 彳 θ # '
-翁仆石卢咸：目丨I哭r u 1一符別疋，使用一般 一乳化反感測(非分散紅外線二氧曲 。該感測器具有對檢驗液添加酸而產生i1H)、 紅外線檢測所產生的C 〇2之裝置。 2 衣 !產二置r具：丄内磷酸等的無機強酸溶液的氣僧 、將k驗液供給至槽的裝置、將氬等的惰性氣體或 的載氣導入槽内的無機強酸之裝置、以及將槽的淨 氣體輸送至紅外線檢測裝置之裝置。 曰、#-Weng Pu Shi Luxian: I ’m crying, I use a common emulsification counter-sensing (non-dispersive infrared dioxane. This sensor has an acid added to the test solution to generate i1H), an infrared detection station Device for generating C02. 2 clothing! Two sets of equipment: the monk of inorganic strong acid solution such as phosphoric acid, the device to supply k test solution to the tank, the device to introduce an inert gas such as argon or a carrier gas into the tank, And a device for transmitting the net gas of the tank to the infrared detection device. 、、 #
於此c〇2產生裝置中，若將檢驗液導入槽内，則在無機 強酸溶液中’碳酸系鹽類係由離子形成分子狀的co被輸 送至槽的淨空空間中。再隨著載氣經輸送裝置而輸送至紅 外線檢測裝置。於紅外線檢測裝置中，照射對應的1 性吸收波數範圍的紅外線，由吸收強度來測定c^2濃』。 顯像液中的無機碳酸或c〇2的濃度，由於可心$ ^來自 無機碳酸鹽類’故由這些濃度能夠測定鹼性顯像成分的碳In this co2 generating device, if the test solution is introduced into the tank, in the inorganic strong acid solution, carbon dioxide, which is a carbonate-based salt system, is formed into molecules in the form of molecular ions, and is transferred to the headroom of the tank. The carrier gas is then sent to the infrared detection device as it passes through the delivery device. In the infrared detection device, the infrared rays corresponding to the range of the unisex absorption wave number are irradiated, and the c ^ 2 concentration is measured from the absorption intensity ". The concentration of inorganic carbonic acid or CO2 in the developing solution can be determined from the inorganic carbonates because of the reasonable concentration. Therefore, it is possible to determine the carbon content of the alkaline imaging component from these concentrations.
200305794 種濃度 的顯像 夠很容 由該濃 液的運 後稀釋 成分（ 種步驟 既定的 液的回 理，而 或半導 鹼性顯像成分的濃度與碳酸系鹽類的濃 游離的鹼性顯像成分的濃度。如上述，藉 像成分的濃度扣除碳酸系鹽類的濃度，則 性顯像成分的濃度。並且，利用導電率 計、超音波濃度計等的情形，在預先求得 像成分濃度與碳酸系鹽類的濃度以及相當 成分的計測數據之間的關係式中，藉由導 濃度與這些計測值，則能夠得到游離鹼性 測定步驟 活性之驗 易地實現 度測定步 送管線、 步驟中， 游離驗性 下實施濃 顯像活性 收步驟、 能夠有效 體基板在 五、發明說明（11) 酸系鹽類的濃度 若求得全部 度，則能夠求出 由從全部鹼性顯 能夠求得游離鹼 計、相位差濃度 的、游離驗性顯 於全部鹼性顯像 入碳酸系鹽類的 顯像成分濃度。 藉由具備這 夠提供具有正確 管線。因此，能 再就是，藉 像步驟、顯像廢 生步驟、以及最 活性之驗性顯像 此濃度，在此各 了能夠供給具有 確地實施顯像廢 項步驟的濃度管 且，可減少液晶 因。 於第1表中 或濃度測定裝置 性顯像液至顯像 南精確度的顯像 驟或濃度測定裝 回收步驟、濃縮 能夠正確地測定 顯像成分）的濃 度管理，於顯像 之顯像液以外， 濃縮步驟、再生 地施行回收·再 光處理步驟中的 ，首先能 液的供給 步驟。 置，於顯 步驟、再 具有顯像 度。基於 步驟中除 還能夠正 步驟等各 生。並 不良要 基於對應於鹼性顯像液（TMAH )在空氣The 200305794 concentration of imaging is enough to dilute the components after the transportation of the concentrated solution (the process of the liquid in a predetermined step, or the concentration of the semiconducting alkaline imaging component and the concentration of the free basicity of the carbonate salts). The concentration of the imaging component. As described above, the concentration of the imaging component is subtracted from the concentration of the imaging component, and the concentration of the sexual imaging component is obtained. In addition, in the case of a conductivity meter and an ultrasonic densitometer, the image is obtained in advance. In the relational formula between the component concentration, the concentration of carbonate salts, and the measurement data of the equivalent components, the derivative concentration and these measured values can be used to obtain the test of the activity of the free alkaline measurement step, and the step measurement pipeline can be easily realized. In the step, a thick imaging activity recovery step is performed under the free test, and the substrate can be effectively used in the fifth aspect of the invention. (11) If the concentration of the acid-based salt is obtained, the degree of development from all the basics can be obtained. It is possible to determine the concentration of the imaging component of the free base meter, the phase difference concentration, and the freeness of the imaging component, which is more obvious than that of all alkaline imaging into carbonate salts. By having this, it is possible to provide a correct tube. Therefore, the concentration step can be the borrowing step, the imaging waste step, and the most active inspection to visualize the concentration. Here, each concentration tube can be provided to have the development waste step performed. Reduce the liquid crystal factor. Concentration management can be performed in the first table or in the concentration measurement device development solution to the accuracy of the imaging step or the concentration measurement device in the recovery step, and the concentration measurement device can be accurately measured. In addition to the developing solution, in the concentration step and the recovery and re-light treatment step in the regeneration step, the first energy supply step is performed. Place it in the display step, and then have the visibility. In addition to the steps in addition to the steps can also be students. And the bad is based on the corresponding alkaline imaging solution (TMAH) in the air
2042-5562-PF(Nl) ptd 第16頁 200305794 五、發明說明（12) 中靜置之經過時間之中和滴定法以測定全部鹼性顯像液成 分與碳酸鹽的濃度之結果、以及基於二氧化碳測定裝置 (紅外線二氧化碳檢測裝置，以下稱為本法。）以測定碳 酸鹽濃度之結果，將二者加以對比，結果如第1表所示。 【第1表】 辤置時間 中和滴定法 本法 TM AH重量％ 碳酸鹽重量％ 碳酸鹽重量％ 0 2.379 0.013 0.003 30分 2.379 0.019 0.014 如第1表所示，即使經過靜置時間，全部鹼性顯像成 分仍為一定。而相對於基於本法的破酸鹽濃度產生大幅變 化，基於中和滴定法的碳酸鹽濃度變化卻沒那麼大，而在 初始（靜置時間0 )的時點，相較於本法的結果則為顯示 較大值（相差0 · 1 0重量％ )的一方，即使經過3 0分鐘，結 果仍顯示比本法稍高（相差0. 0 0 5重量％ )。若依此情形， 一般認為在中和滴定時的計測時間中，C02溶入試樣溶液 中。因而，根據此結果可證明，於測定操作中，對於因吸 收二氧化碳所產生的碳酸鹽進行滴定的現象。 發明效果： 若依據本發明，則能夠正確地控制含有鹼性顯像成分 之顯像液的濃度，並提供一種用以達成正確而有效的顯像 步驟之顯像液的濃度測定技術。又基於此種濃度測定技 術，能夠提供一種有效的鹼性顯像液的濃度管理、鹼性顯2042-5562-PF (Nl) ptd Page 16 200305794 V. Description of the invention (12) The result of standing by neutralization and titration to determine the concentration of all alkaline imaging solution components and carbonates, and based on A carbon dioxide measuring device (infrared carbon dioxide detecting device, hereinafter referred to as this method). The results of measuring the carbonate concentration are compared, and the results are shown in Table 1. [Table 1] Settling time neutralization titration method This method TM AH wt% Carbonate wt% Carbonate wt% 0 2.379 0.013 0.003 30 minutes 2.379 0.019 0.014 As shown in Table 1, all the alkalis even after the standing time elapses Sex imaging components are still constant. Compared with the method based on this method, the concentration of the broken salt has changed greatly, but the carbonate concentration based on the neutralization titration method has not changed so much. At the initial (resting time 0) point, compared with the result of this method, In order to display a larger value (a difference of 0 · 10% by weight), even if 30 minutes have passed, the result is still slightly higher than this method (a difference of 0.05% by weight). If this is the case, it is generally believed that during the measurement time of the neutralization titration, C02 is dissolved in the sample solution. Therefore, from this result, it can be proved that during the measurement operation, the titration of the carbonate generated by the absorption of carbon dioxide is performed. ADVANTAGE OF THE INVENTION According to this invention, the density | concentration of the developing solution containing an alkaline developing component can be controlled correctly, and the technique for measuring the density of a developing solution for achieving a correct and effective developing process is provided. Based on this concentration measurement technology, it can provide an effective concentration management and alkaline development solution.
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| JP4366490B2 (en) * | 2003-08-22 | 2009-11-18 | 長瀬産業株式会社 | Developer supply method and apparatus |
| JP2006189646A (en) * | 2005-01-06 | 2006-07-20 | Nagase & Co Ltd | Method for removing carbonate in resist developing solution, removing device, and method for controlling concentration of resist developing solution |
| JP5000246B2 (en) * | 2005-09-28 | 2012-08-15 | 株式会社半導体エネルギー研究所 | Waste liquid treatment method and treatment apparatus |
| JP6721157B2 (en) * | 2015-07-22 | 2020-07-08 | 株式会社平間理化研究所 | Method and apparatus for measuring component concentration of developer, and method and apparatus for managing developer |
| JP6551784B2 (en) * | 2015-08-31 | 2019-07-31 | パナソニックＩｐマネジメント株式会社 | Method and apparatus for managing carbonic acid concentration in resist stripping solution |
| JP6551787B2 (en) * | 2015-09-28 | 2019-07-31 | パナソニックＩｐマネジメント株式会社 | Method and apparatus for managing carbonic acid concentration in resist stripping solution |
| CN106596840B (en) * | 2016-12-15 | 2019-01-22 | 深圳市华星光电技术有限公司 | Developer solution concentration of lye measurement method and adjusting method |
| JP2018120901A (en) * | 2017-01-23 | 2018-08-02 | 株式会社平間理化研究所 | Development device |
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| JP4097973B2 (en) | 2008-06-11 |
| TWI313794B (en) | 2009-08-21 |
| KR100916986B1 (en) | 2009-09-14 |
| JP2003295470A (en) | 2003-10-15 |
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