WO2015143768A1 - 一种测量剥离液中光阻的浓度的方法 - Google Patents
一种测量剥离液中光阻的浓度的方法 Download PDFInfo
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- WO2015143768A1 WO2015143768A1 PCT/CN2014/078266 CN2014078266W WO2015143768A1 WO 2015143768 A1 WO2015143768 A1 WO 2015143768A1 CN 2014078266 W CN2014078266 W CN 2014078266W WO 2015143768 A1 WO2015143768 A1 WO 2015143768A1
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- 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
- G01N21/33—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using ultraviolet light
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N1/00—Sampling; Preparing specimens for investigation
- G01N1/28—Preparing specimens for investigation including physical details of (bio-)chemical methods covered elsewhere, e.g. G01N33/50, C12Q
- G01N1/38—Diluting, dispersing or mixing samples
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- 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
- G01N21/314—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry with comparison of measurements at specific and non-specific wavelengths
- G01N2021/3155—Measuring in two spectral ranges, e.g. UV and visible
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N2201/00—Features of devices classified in G01N21/00
- G01N2201/12—Circuits of general importance; Signal processing
- G01N2201/13—Standards, constitution
Definitions
- the present invention relates to a method of measuring the concentration of photoresist in a stripper. Background technique
- Photoresist is widely used in the formation of mask patterns in the TFT industry.
- the photoresist can be classified into a negative photoresist and a positive photoresist. After the positive photoresist is exposed, the exposed portion becomes more soluble in the developer, and the unexposed portion leaves a pattern on the substrate.
- the positive photoresist content in the Stripper is usually measured by UV-Vis spectrophotometry (UV-VIS).
- UV-VIS UV-Vis spectrophotometry
- Existing methods for measuring the concentration of photoresist in a stripper are typically direct reading of the absorbance method and creation of a database. However, this method is complicated to operate and has little meaning for application. Summary of the invention
- An object of the present invention is to provide a method for measuring the concentration of photoresist in a peeling liquid which can more accurately measure the concentration of photoresist in the stripping solution.
- a method of measuring the concentration of photoresist in a stripping solution comprising the steps of:
- S106 Perform n-th order derivation on the collected vocabulary, obtain and store an nth-order derivative curve, where n is an integer greater than or equal to 1;
- S108 Establish a standard curve based on the obtained nth order derivative curve, and calculate the concentration of the photoresist of the sample to be tested.
- the photoresist is coated on the plain glass, and after the exposure process, the development process, and the etching process, the photoresist is scraped to the target quality, and the peeling process is simulated in the beaker to obtain the target. Standard of concentration.
- the spectrum of the sample and the sample to be tested is collected by an ultraviolet-visible spectrophotometer.
- the S104 includes the following steps:
- Solvent selection Select a suitable solvent and use the solvent as a test reference solution
- Stripping liquid vocabulary set Take a certain amount of fresh stripping solution, and after using the solvent to dilute a certain multiple, scan the absorption curve in the same wavelength range;
- Standard spectral set a standard of multiple target concentrations, after diluting the multiple with the solvent, scanning the absorption curve in the same wavelength range;
- Sample Spectrometry The sample to be tested is taken, and after diluting the multiple with the solvent, the absorption curve in the same wavelength range is scanned.
- the absorption curve of the fresh stripping solution, the standard sample and the sample to be tested is subjected to n-th order derivative conversion, and each converted nth order derivative curve is saved, wherein n Is 1, 2, 3 or 4.
- the standard curve is established by the valley value at the first wavelength and the concentration of the photoresist of the standard.
- the standard sample and the sample to be tested are in the third wave.
- a standard curve is established with the amplitude of the third to fourth wavelengths and the concentration of the photoresist of the standard.
- the stripping liquid is an organic amine stripping liquid.
- the photoresist is a phenolic resin-based positive photoresist.
- the beneficial effects of the present invention are: In the method for measuring the concentration of the photoresist in the stripping solution of the present invention, the photoresist standard is prepared first; then the standard sample and the spectrum corresponding to the sample to be tested are collected; and then the spectrum of the sample is collected Performing the nth order derivation, obtaining and storing the nth order derivation curve, where n is an integer greater than or equal to 1; finally, based on the obtained nth order derivation curve, a standard curve is established, and the photoresist of the sample to be tested is calculated. concentration. Based on the established standard curve, the concentration of photoresist in the stripping solution can be more accurately determined.
- FIG. 1 is a schematic illustration of the steps of preparing a photoresist standard in a method of measuring the concentration of photoresist in a stripper according to an embodiment of the present invention
- Figure 2 is a view showing the formation of a trough at the ⁇ 1 obtained by the nth-order derivative curve obtained by the method for measuring the concentration of the photoresist in the stripping liquid according to a specific embodiment of the present invention
- Figure 3 is a view showing the formation of a peak at ⁇ 2 of the nth-order derivative curve obtained by the method for measuring the concentration of the photoresist in the stripping liquid according to a specific embodiment of the present invention
- Figure 4 is a view showing the formation of a trough at ⁇ 3 and formation of a peak at ⁇ 4 in the method of measuring the concentration of photoresist in the stripping solution according to a specific embodiment of the present invention
- Figure 5 is a flow diagram of a method of measuring the concentration of photoresist in a stripper in accordance with an embodiment of the present invention. detailed description
- the method for measuring the concentration of the photoresist in the stripping liquid of the present embodiment includes the following steps:
- S106 performing an n-th order derivation on the collected corpora, obtaining and storing an nth-order derivative curve, where ⁇ is an integer greater than or equal to 1;
- S108 Establish a standard curve based on the obtained nth-order derivative curve, and calculate the concentration of the photoresist of the sample to be tested.
- the stripping liquid is an organic amine stripping solution.
- the photoresist is a phenolic resin-based positive photoresist.
- the photoresist is coated on the plain glass (step ⁇ ), and the exposure process (step ⁇ ), the development process (step C), and the etching process (step D) are performed, and the light is applied. Scratch the target mass and simulate the stripping process in the beaker to obtain the target concentration standard (step F).
- the design and control of other process parameters must be identical to the parameters on the actual production line, except that the glass coated with the photoresist does not need to be pre-plated with a metal film or a non-metal film layer.
- the standard sample and the optical term of the sample to be tested are collected by an ultraviolet-visible spectrophotometer.
- the S104 includes the following steps:
- Solvent selection According to the solubility and chemical properties of the components of the stripping solution, combined with economy and safety, select a suitable solvent, and use the solvent as a test reference liquid;
- Baseline scan The reference cell is referenced by the solvent, the solvent is placed in the sample cell, the baseline is scanned in the visible region-ultraviolet region, and the scan curve is saved;
- Stripping liquid vocabulary set Take a certain amount of fresh stripping solution, dilute a certain number of times with the solvent, scan the absorption curve in the same wavelength range, and save;
- Standard Spectral Collection A standard of multiple target concentrations (for example, 3 to 5), after diluting the multiple with the solvent, scanning the absorption curve in the same wavelength range and saving;
- Sample Spectrometry The sample to be tested is taken, and after diluting the multiple with the solvent, the absorption curve in the same wavelength range is scanned and saved.
- the absorption curve of the fresh stripping solution, the standard sample and the sample to be tested is subjected to n-th order derivative conversion, and each converted nth order derivative curve is saved, where n is, for example, 1, 2, 3 Or 4.
- n is, for example, 1, 2, 3 Or 4.
- the order is derived and used as a graph software for curve fitting.
- the concentration of the photoresist in the stripping solution as the test sample can be calculated.
- the concentration of the photoresist in the stripping solution can be accurately determined, so that the ability of the stripping solution to peel off the photoresist can be intuitively grasped, and the time for changing the liquid solution can be determined according to the actual photoresist concentration in the stripping solution. It is of great significance for the improvement of the service life of the stripper and can be widely used in the TFT industry.
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Abstract
一种利用紫外-可见分光光度计测量剥离液中光阻的浓度的方法。该测量剥离液中光阻的浓度的方法具有以下步骤:S102:制备光阻标样;S104:采集标样及待测试的样品对应的光谱;S106:对所采集的光谱进行n阶求导,得到并存储第n阶求导曲线,其中n为大于或等于1的整数;和S108:基于所得到的第n阶求导曲线建立标准曲线,计算待测试的样品的光阻的浓度。根据建立的标准曲线,即可准确计算出作为测试样品的剥离液中光阻的浓度。
Description
一种测量剥离液中光阻的浓度的方法 技术领域
本发明涉及一种测量剥离液中光阻的浓度的方法。 背景技术
光阻( Photoresist, 简称 PR )广泛应用于 TFT行业中各膜层掩膜图案的形成。
说
光阻可分为负型光阻和正型光阻。 正型光阻经曝光后, 其曝光部分会变得更加容 易溶于显影液中, 而未曝光部分在基板上留下图案。
剥离液( Stripper )中的正型光阻含量通常书釆用紫外-可见分光光度法( UV-VIS ) 测量。 现有的测量剥离液中光阻的浓度的方法通常为直接读取吸光度法并建立数 据库。 但这种方法操作复杂, 应用意义不大。 发明内容
本发明的目的在于, 提供一种测量剥离液中光阻的浓度的方法, 其可更准确 地测定剥离液中光阻的浓度。
本发明通过如下技术方案实现: 一种测量剥离液中光阻的浓度的方法, 所述 测量剥离液中光阻的浓度的方法包括以下步骤:
S102: 制备光阻标样;
S 104: 釆集标样及待测试的样品对应的光语;
S106: 对所釆集的光语进行 n阶求导, 得到并存储第 n阶求导曲线, 其中 n 为大于或等于 1的整数; 和
S108: 基于所得到的第 n阶求导曲线建立标准曲线, 计算待测试的样品的光 阻的浓度。
作为上述技术方案的进一步改进, 所述 S102中, 将光阻涂布在素玻璃上, 经 过曝光制程、 显影制程和蚀刻制程, 将光阻刮取目标质量, 在烧杯中模拟剥离过 程, 得到目标浓度的标样。
作为上述技术方案的进一步改进,所述 S104中,利用紫外 -可见分光光度计釆 集标样及待测试的样品的光谱。
作为上述技术方案的进一步改进, 所述 S104包括以下步骤:
溶剂选择: 选择合适的溶剂, 并以该溶剂为测试参比液;
剥离液光语釆集: 取一定量的新鲜剥离液, 用所述溶剂稀释一定倍数后, 扫 描在相同波长范围内的吸收曲线;
标样光谱釆集: 将多个目标浓度的标样, 用所述溶剂稀释所述倍数后, 扫描 在相同波长范围内的吸收曲线;
样品光谱釆集: 取待测试的样品, 用所述溶剂稀释所述倍数后, 扫描在相同 波长范围内的吸收曲线。
作为上述技术方案的进一步改进, 所述 S106中, 将新鲜剥离液、 标样以及待 测试的样品的吸收曲线进行 n阶求导转换, 并保存各个转换后的第 n阶求导曲线, 其中 n为 1、 2、 3或 4。
作为上述技术方案的进一步改进, 所述 S108中, 当新鲜剥离液的第 n阶求导 曲线在第一波长处吸收为 0, 而标样及待测试的样品在第一波长处有一致波谷时, 以第一波长处波谷值与标样的光阻的浓度建立标准曲线。
作为上述技术方案的进一步改进, 所述 S108中, 当新鲜剥离液的第 n阶求导 曲线在第二波长处吸收为 0, 而标样及待测试的样品在第二波长处有一致波峰时, 以第二波长处波峰值与标样的光阻的浓度建立标准曲线。
作为上述技术方案的进一步改进, 所述 S108中, 当新鲜剥离液的第 n阶求导 曲线在第三波长至第四波长区间吸收均为 0,而标样及待测试的样品在第三波长处 有一致波谷且在第四波长处有一致波峰时, 以第三波长至第四波长的振幅与标样 的光阻的浓度建立标准曲线。
作为上述技术方案的进一步改进, 所述剥离液为有机胺类剥离液。
作为上述技术方案的进一步改进, 所述光阻为酚酸树脂类正型光阻。
本发明的有益效果是: 本发明的测量剥离液中光阻的浓度的方法中, 先制备 光阻标样; 接着釆集标样及待测试的样品对应的光谱; 然后对所釆集的光谱进行 n 阶求导, 得到并存储第 n阶求导曲线, 其中 n为大于或等于 1的整数; 最后基于 所得到的第 n阶求导曲线建立标准曲线, 计算待测试的样品的光阻的浓度。 依据 建立好的标准曲线, 可更准确地测定剥离液中光阻的浓度。
附图说明 ,
图 1是根据本发明的一个具体实施例的测量剥离液中光阻的浓度的方法中制 备光阻标样的步骤的示意图;
图 2是显示本发明的一个具体实施例的测量剥离液中光阻的浓度的方法中得 到的第 n阶求导曲线在 λ 1处形成波谷的示意图;
图 3是显示本发明的一个具体实施例的测量剥离液中光阻的浓度的方法中得 到的第 η阶求导曲线在 λ 2处形成波峰的示意图;
图 4是显示本发明的一个具体实施例的测量剥离液中光阻的浓度的方法中得 到的第 η阶求导曲线在 λ 3处形成波谷并在 λ 4处形成波峰的示意图;
图 5是根据本发明的一个具体实施例的测量剥离液中光阻的浓度的方法的流 程示意图。 具体实施方式
以下结合附图对本发明的具体实施方式进行进一步的说明。
如图 1至图 5所示, 本实施例的测量剥离液中光阻的浓度的方法包括以下步 骤:
S102: 制备光阻标样;
S 104: 釆集标样及待测试的样品对应的光语;
S106: 对所釆集的光语进行 η阶求导, 得到并存储第 η阶求导曲线, 其中 η 为大于或等于 1的整数; 和
S108: 基于所得到的第 η阶求导曲线建立标准曲线, 计算待测试的样品的光 阻的浓度。
在本实施例中, 所述剥离液为有机胺类剥离液。 所述光阻为酚酸树脂类正型 光阻。
如图 1所示, 在所述 S102中, 将光阻涂布在素玻璃上(步骤 Α ), 经过曝光 制程(步骤 Β )、显影制程(步骤 C )和蚀刻制程(步骤 D ), 将光阻刮取目标质量, 在烧杯中模拟剥离过程, 得到目标浓度的标样(步骤 F )。 标样制备过程中, 除用 于涂布光阻的素玻璃不需要预先镀好金属膜或非金属膜层外, 其他制程参数的设 计与控制均需与实际产线上的参数完全一致。
在所述 S104中, 利用紫外-可见分光光度计釆集标样及待测试的样品的光语。
其中, 所述 S104包括以下步骤:
溶剂选择: 根据剥离液组分的溶解性质与化学性质, 并结合经济、 安全性, 选择合适的溶剂, 并以该溶剂为测试参比液;
基线扫描: 参比池以所述溶剂为参比, 样品池放置溶剂, 在可见光区-紫外光 区扫描基线, 并保存扫描曲线;
剥离液光语釆集: 取一定量的新鲜剥离液, 用所述溶剂稀释一定倍数后, 扫 描在相同波长范围内的吸收曲线, 并保存;
标样光谱釆集: 将多个目标浓度的标样 (例如 3至 5个), 用所述溶剂稀释所 述倍数后, 扫描在相同波长范围内的吸收曲线, 并保存;
样品光谱釆集: 取待测试的样品, 用所述溶剂稀释所述倍数后, 扫描在相同 波长范围内的吸收曲线, 并保存。
在所述 S106中, 将新鲜剥离液、 标样以及待测试的样品的吸收曲线进行 n阶 求导转换, 并保存各个转换后的第 n阶求导曲线, 其中 n例如为 1、 2、 3或 4。 其 中, 可以釆用紫外 -可见分光光度计操作软件自带的 "求导" 功能, 直接进行第 n 阶求导转换; 也可以釆用 "吸光度-波长" 的原始值进行积分逐级至第 n阶求导, 并用作图软件进行曲线拟合。
在所述 S108中, 当新鲜剥离液的第 n阶求导曲线在第一波长 λ 1处吸收为 0, 而标样及待测试的样品在第一波长 λ ΐ处有一致波谷时, 如图 2所示, 以第一波长 λ 1处波谷值与标样的光阻的浓度建立标准曲线。
在所述 S108中, 当新鲜剥离液的第 η阶求导曲线在第二波长 λ 2处吸收为 0, 而标样及待测试的样品在第二波长 λ 2处有一致波峰时, 如图 3所示, 以第二波长 λ 2处波峰值与标样的光阻的浓度建立标准曲线。
在所述 S108中, 当新鲜剥离液的第 η阶求导曲线在第三波长 λ 3至第四波长 λ 4区间吸收均为 0, 而标样及待测试的样品在第三波长 λ 3处有一致波谷且在第 四波长 λ 4处有一致波峰时, 如图 4所示, 以第三波长 λ 3至第四波长 λ 4的振幅 与标样的光阻的浓度建立标准曲线。
根据以上建立好的标准曲线(通常为直线), 即可计算出作为测试样品的剥离 液中光阻的浓度。 以这种方式, 可以准确测定剥离液中光阻的浓度, 便于直观掌 握剥离液剥离光阻的能力, 可才艮据剥离药液中实际光阻浓度判定更换药液的时间,
对剥离液使用寿命的提升有重要意义, 可广泛用于 TFT行业。
以上具体实施方式对本发明进行了详细的说明, 但这些并非构成对本发明的 限制。 本发明的保护范围并不以上述实施方式为限, 但凡本领域普通技术人员根 据本发明所揭示内容所作的等效修饰或变化, 皆应纳入权利要求书中记载的保护 范围内。
Claims
1、 一种测量剥离液中光阻的浓度的方法, 其中, 所述测量剥离液中光阻的浓 度的方法包括以下步骤:
S102: 制备光阻标样;
S 104: 釆集标样及待测试的样品对应的光语;
S106: 对所釆集的光语进行 n阶求导, 得到并存储第 n阶求导曲线, 其中 n 为大于或等于 1的整数; 和
S108: 基于所得到的第 n阶求导曲线建立标准曲线, 计算待测试的样品的光 阻的浓度。
2、根据权利要求 1所述的测量剥离液中光阻的浓度的方法, 其中, 所述 S102 中, 将光阻涂布在素玻璃上, 经过曝光制程、 显影制程和蚀刻制程, 将光阻刮取 目标质量, 在烧杯中模拟剥离过程, 得到目标浓度的标样。
3、根据权利要求 1所述的测量剥离液中光阻的浓度的方法, 其中, 所述 S104 中, 利用紫夕卜可见分光光度计釆集标样及待测试的样品的光语。
4、根据权利要求 1所述的测量剥离液中光阻的浓度的方法, 其中, 所述 S104 包括以下步骤:
溶剂选择: 选择合适的溶剂, 并以该溶剂为测试参比液;
剥离液光语釆集: 取一定量的新鲜剥离液, 用所述溶剂稀释一定倍数后, 扫 描在相同波长范围内的吸收曲线;
标样光谱釆集: 将多个目标浓度的标样, 用所述溶剂稀释所述倍数后, 扫描 在相同波长范围内的吸收曲线;
样品光谱釆集: 取待测试的样品, 用所述溶剂稀释所述倍数后, 扫描在相同 波长范围内的吸收曲线。
5、根据权利要求 4所述的测量剥离液中光阻的浓度的方法, 其中, 所述 S106 中, 将新鲜剥离液、 标样以及待测试的样品的吸收曲线进行 n阶求导转换, 并保 存各个转换后的第 n阶求导曲线, 其中 n为 1、 2、 3或 4。
6、根据权利要求 5所述的测量剥离液中光阻的浓度的方法, 其中, 所述 S108
中, 当新鲜剥离液的第 n阶求导曲线在第一波长处吸收为 0, 而标样及待测试的样 品在第一波长处有一致波谷时, 以第一波长处波谷值与标样的光阻的浓度建立标 准曲线。
7、根据权利要求 5所述的测量剥离液中光阻的浓度的方法, 其中, 所述 S108 中, 当新鲜剥离液的第 n阶求导曲线在第二波长处吸收为 0, 而标样及待测试的样 品在第二波长处有一致波峰时, 以第二波长处波峰值与标样的光阻的浓度建立标 准曲线。
8、根据权利要求 5所述的测量剥离液中光阻的浓度的方法, 其中, 所述 S108 中, 当新鲜剥离液的第 n阶求导曲线在第三波长至第四波长区间吸收均为 0, 而标 样及待测试的样品在第三波长处有一致波谷且在第四波长处有一致波峰时, 以第 三波长至第四波长的振幅与标样的光阻的浓度建立标准曲线。
9、 根据权利要求 6所述的测量剥离液中光阻的浓度的方法, 其中, 所述剥离 液为有机胺类剥离液。
10、 根据权利要求 7所述的测量剥离液中光阻的浓度的方法, 其中, 所述剥 离液为有机胺类剥离液。
11、 根据权利要求 8 所述的测量剥离液中光阻的浓度的方法, 其中, 所述剥 离液为有机胺类剥离液。
12、 根据权利要求 6所述的测量剥离液中光阻的浓度的方法, 其中, 所述光 阻为酚酸树脂类正型光阻。
13、 根据权利要求 7所述的测量剥离液中光阻的浓度的方法, 其中, 所述光 阻为酚酸树脂类正型光阻。
14、 根据权利要求 8所述的测量剥离液中光阻的浓度的方法, 其中, 所述光 阻为酚酸树脂类正型光阻。
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| JPH06331541A (ja) * | 1993-03-24 | 1994-12-02 | Kurabo Ind Ltd | 有機剥離液の成分濃度測定方法およびその測定装置 |
| CN1439120A (zh) * | 2000-12-30 | 2003-08-27 | 东进半导体化学株式会社 | 基于近红外分光计控制光致抗蚀剂剥离过程的方法和再生光致抗蚀剂剥离剂成分的方法 |
| CN102435547A (zh) * | 2011-09-15 | 2012-05-02 | 上海华力微电子有限公司 | 敏感光阻耐受程度检测方法及晶圆缺陷检验方法 |
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| JPH06331541A (ja) * | 1993-03-24 | 1994-12-02 | Kurabo Ind Ltd | 有機剥離液の成分濃度測定方法およびその測定装置 |
| CN1439120A (zh) * | 2000-12-30 | 2003-08-27 | 东进半导体化学株式会社 | 基于近红外分光计控制光致抗蚀剂剥离过程的方法和再生光致抗蚀剂剥离剂成分的方法 |
| CN102435547A (zh) * | 2011-09-15 | 2012-05-02 | 上海华力微电子有限公司 | 敏感光阻耐受程度检测方法及晶圆缺陷检验方法 |
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