CN103196868A - Determination method of refractive index of photoresist - Google Patents
Determination method of refractive index of photoresist Download PDFInfo
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- CN103196868A CN103196868A CN2013101226405A CN201310122640A CN103196868A CN 103196868 A CN103196868 A CN 103196868A CN 2013101226405 A CN2013101226405 A CN 2013101226405A CN 201310122640 A CN201310122640 A CN 201310122640A CN 103196868 A CN103196868 A CN 103196868A
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- refractive index
- terahertz
- phase place
- assay method
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- 229920002120 photoresistant polymer Polymers 0.000 title claims abstract description 88
- 238000000034 method Methods 0.000 title abstract description 8
- 238000001328 terahertz time-domain spectroscopy Methods 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 238000005259 measurement Methods 0.000 claims abstract description 11
- 230000005684 electric field Effects 0.000 claims abstract description 9
- 239000007788 liquid Substances 0.000 claims abstract description 5
- 238000010438 heat treatment Methods 0.000 claims abstract description 4
- 238000003556 assay Methods 0.000 claims description 22
- 239000008367 deionised water Substances 0.000 claims description 5
- 229910021641 deionized water Inorganic materials 0.000 claims description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical group [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 3
- 229910052782 aluminium Inorganic materials 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 4
- 239000010409 thin film Substances 0.000 abstract 3
- 206010034972 Photosensitivity reaction Diseases 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000002360 preparation method Methods 0.000 description 3
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 2
- 229910007709 ZnTe Inorganic materials 0.000 description 2
- 239000000463 material Substances 0.000 description 2
- 230000003287 optical effect Effects 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 238000005950 photosensitized reaction Methods 0.000 description 2
- 239000011347 resin Substances 0.000 description 2
- 229920005989 resin Polymers 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000002925 chemical effect Effects 0.000 description 1
- 230000019771 cognition Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000010894 electron beam technology Methods 0.000 description 1
- 238000005538 encapsulation Methods 0.000 description 1
- 239000003292 glue Substances 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000004615 ingredient Substances 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 238000005457 optimization Methods 0.000 description 1
- 238000000016 photochemical curing Methods 0.000 description 1
- 230000002165 photosensitisation Effects 0.000 description 1
- 239000003504 photosensitizing agent Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000002861 polymer material Substances 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
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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
- G01N21/35—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light
- G01N21/3581—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation
- G01N21/3586—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry using infrared light using far infrared light; using Terahertz radiation by Terahertz time domain spectroscopy [THz-TDS]
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- Physics & Mathematics (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
Abstract
The invention relates to a determination method of a refractive index of photoresist. The determination method comprises the following steps of: condensing photoresist liquid on a water surface to obtain a photoresist thin film; placing the photoresist thin film into an annular bracket and heating the photoresist thin film to obtain a sample bracket; only determining a time waveform of a pulse electric field after terahertz electromagnetic waves pass through the blank annular bracket by utilizing a terahertz time-domain spectroscopy system; carrying out Fourier conversion to obtain a referred phase; determining a time waveform of the pulse electric field after the terahertz electromagnetic waves pass through the sample bracket by utilizing the terahertz time-domain spectroscopy system; carrying out the Fourier conversion to obtain a sample phase; obtaining a phase difference according to the referred phase and the sample phase; and obtaining the refractive index of the photoresist in a terahertz frequency range according to a calculation formula. The photoresist is not sensitive to the terahertz electromagnetic waves so that a photosensitive reaction does not happen and the refractive index of the photoresist in the terahertz frequency range can be accurately measured in real time before and after exposure. The determination method disclosed by the invention is convenient and rapid; and a testing result is accurate and a measurement range of the refractive index of the photoresist is expanded.
Description
Technical field
The present invention relates to a kind of assay method of photoresist refractive index.
Technical background
Photoresist is the macromolecule polymer material that a class has photosensitizing chemical effect (or to electron energy sensitivity), owing to possess smaller capillary characteristic, makes photoresist have good flowability and homogeneity.
Photoresist claims photoresist again, the photosensitive mixing material of being made up of photosensitive resin, sensitizer and three kinds of principal ingredients of solvent.Photosensitive resin is after illumination, photocuring reaction can take place soon in the exposure area, making the physical property, particularly dissolubility, affinity etc. of this material that significant change take place, is the media that shifts uv-exposure or electron beam exposure pattern, therefore at integrated circuit, encapsulation, MEMS (micro electro mechanical system), optoelectronic device photonic device, flat-panel monitor, fields such as photovoltaic have obtained using widely.
How accurately to obtain the refractive index of photoresist, for the design of device, structure optimization etc. have very important significance.The instrument of modal measurement photoresist refractive index is to use Abbe refractometer.
But the wave band of the measurement refractive index of Abbe refractometer is shorter, DR-M2 multi-wavelength Abbe refractometer for example, and the measurement wave band is 450nm-1100nm.Because the measurement wave band of this Abbe refractometer is limited, so can not measure the problem of photoresist refractive index in the Terahertz frequency range.In addition, Abbe refractometer is relatively responsive to terahertz electromagnetic wave, easily photosensitive reflection takes place and produce error in measuring process.
Summary of the invention
The present invention carries out in order to address the above problem, and purpose is to provide a kind of assay method that can accurately measure the photoresist refractive index of the refractive index of photoresist in the Terahertz frequency range.
The present invention has adopted following steps to achieve these goals:
The invention provides a kind of assay method of photoresist refractive index, it is characterized in that, may further comprise the steps:
(1). photoresist liquid is dropped on the water surface, obtain photoresist film after solidifying, measure the thickness of photoresist film;
(2). place the hollow bulb of back-shaped support and heating to obtain sample holder photoresist film;
(3). use the terahertz time-domain spectroscopy system only to measure the time waveform of the impulse electric field of terahertz electromagnetic wave after by blank back-shaped support, by obtaining phase place after the fourier transform and as with reference to phase place;
(4). use terahertz time-domain spectroscopy system measurement terahertz electromagnetic wave by the time waveform of the impulse electric field behind the sample holder, by obtaining phase place after the fourier transform and as the sample phase place;
(5). obtain phase differential according to reference phase place and sample phase place;
(6). obtain the refractive index of photoresist in the Terahertz frequency range according to default computing formula;
Wherein, computing formula is:
In computing formula, n
sBe the refractive index of photoresist in the Terahertz frequency range, n
rBe the refractive index of object of reference in the back-shaped support of blank, object of reference is air, n
rValue to be made as 1, c be terahertz electromagnetic wave velocity of propagation in a vacuum, occurrence is 3 * 10
8M/s.F is the frequency of terahertz electromagnetic wave, and occurrence is 0.1～10 THz, and d is the thickness of photoresist film, and Δ φ is the phase differential in the Terahertz frequency range with reference to phase place and sample phase place.
In addition, in the assay method of photoresist refractive index of the present invention, such feature can also be arranged: in step (1), water is deionized water, the thickness of photoresist film is 92 μ m and 146 μ m, the type of photoresist is AZ 1500, and service precision is the thickness that the electronic microcalliper of 0.001 mm is measured photoresist film.
In addition, in the assay method of photoresist refractive index of the present invention, such feature can also be arranged: in step (2), back-shaped support is aluminum products.
In addition, in the assay method of photoresist refractive index of the present invention, such feature can also be arranged: in step (3) and step (4), the wavelength of the femtosecond pulse of terahertz time-domain spectroscopy system is 800 nm, and pulsewidth is 100 fs, and repetition frequency is 80 MHz.
Further, in the assay method of photoresist refractive index of the present invention, such feature can also be arranged: in step (5), phase differential is the absolute value with reference to the difference of phase place and sample phase place.
Further, in the assay method of photoresist refractive index of the present invention, such feature can also be arranged: in step (6), the occurrence of the frequency of terahertz electromagnetic wave is 0.2～2THz.
Effect and the effect of invention
The assay method of photoresist refractive index according to the present invention, what the present invention measured is that photoresist is in the refractive index of terahertz electromagnetic wave, because photoresist is insensitive to terahertz electromagnetic wave, so photosensitized reaction can not take place, can realize accurately measuring the refractive index of exposure front and back photoresist in the Terahertz frequency range.The invention process is convenient and swift, and test result is accurate, has expanded the measurement range of photoresist refractive index.
Description of drawings
Fig. 1 is the preparation synoptic diagram of the photoresist film of the embodiment of the invention.
Fig. 2 is the structural representation of the sample holder of the embodiment of the invention.
Fig. 3 is the structural representation of the terahertz time-domain spectroscopy system of the embodiment of the invention.
Fig. 4 is the index of refraction diagram of photoresist in 0.2～2THz frequency range of the embodiment of the invention.
Embodiment
Be described in detail below in conjunction with the assay method of accompanying drawing to the photoresist refractive index that the present invention relates to.Present embodiment is being to implement under the prerequisite with the technical solution of the present invention, and given detailed embodiment and process are to further specify of the present invention, rather than limit the scope of the invention.
Embodiment one
In embodiment one, the assay method of photoresist refractive index of the present invention may further comprise the steps:
Fig. 1 is the preparation synoptic diagram of the photoresist film of the embodiment of the invention one.
(1). as shown in Figure 1, use glue head dropper 3 that photoresist liquid is dropped on the water surface of deionized water 1, photoresist liquid cognition is membranaceous in water surface diffusion, obtains photoresist film 2 after solidifying, and measures the thickness d of photoresist film.
Fig. 2 is the structural representation of the sample holder of the embodiment of the invention one.
(2). as shown in Figure 2, photoresist film is fixed on the hollow bulb of back-shaped support 4, in the oven for baking heating, obtains sample holder.
(3). use the terahertz time-domain spectroscopy system only to measure the time waveform of the impulse electric field of terahertz electromagnetic wave after by blank back-shaped support 4, by obtaining phase place after the fourier transform and as with reference to phase place;
Fig. 3 is the structural representation of the terahertz time-domain spectroscopy system of the embodiment of the invention one.
(4). as shown in Figure 3, use terahertz time-domain spectroscopy system measurement terahertz electromagnetic wave by the time waveform of the impulse electric field behind the sample holder 5, by obtaining phase place after the fourier transform and as the sample phase place;
(5). obtain phase differential according to reference phase place and sample phase place;
(6). obtain the refractive index of photoresist in the Terahertz frequency range according to computing formula;
Wherein, computing formula is:
In this computing formula, n
sBe the refractive index of photoresist in the Terahertz frequency range.
n
rBe the refractive index of object of reference in the back-shaped support of blank, object of reference is air, n
rValue be made as 1.
C is terahertz electromagnetic wave velocity of propagation in a vacuum, and occurrence is 3 * 10
8M/s.
F is the frequency of terahertz electromagnetic wave, and occurrence is 0.1～10THz.
D is the thickness of photoresist film, and the thickness in the present embodiment is 92 μ m.
Δ φ is the phase differential under terahertz electromagnetic wave with reference to phase place and sample phase place, and this phase differential changes along with the frequency change of terahertz electromagnetic wave.
In the step (1) of present embodiment, the type of photoresist is AZ 1500.Deionized water is adopted in preparation during photoresist film 2, because deionized water does not have impurity, can any chemical reaction not take place with photoresist, is conducive to guarantee the reliability for preparing.Service precision is the thickness that the electronic microcalliper of 0.001 mm is measured photoresist film.
In the step (2) of present embodiment, back-shaped support 4 is aluminum products.
In the step (3) and step (4) of present embodiment, the terahertz time-domain spectroscopy system is transmission-type terahertz time-domain spectroscopy system.The wavelength of the femtosecond pulse of this terahertz time-domain spectroscopy system is 800 nm, and pulsewidth is 100 fs, and repetition frequency is 80 MHz.
In the step (5) of present embodiment, phase differential is the absolute value with reference to the difference of phase place and sample phase place.
In the step (6) of present embodiment, this computing formula derives out by Fourier transform and Fresnel formula.
The principle of the terahertz time-domain spectroscopy system measurement refractive index of the embodiment of the invention is as follows:
As shown in Figure 3, the terahertz time-domain spectroscopy system comprises High Resistivity Si 6, chopper 7, GaAs photoconductive antenna 8, four paraboloidal mirrors 9, electro-optic crystal ZnTe 10, Wollaston prism 11, time-delay mechanism 12, beam splitter 13, half-wave plate 14, polaroid 15 and quarter-wave plates 16.
The femto-second laser pulse that femtosecond laser emits is divided into pump light I and surveys light II by beam splitter 13, incides on the GaAs photoconductive antenna behind pump light I process half-wave plate 14 and the chopper 7 and produces terahertz electromagnetic wave.Survey light II through time-delay mechanism 12 by 15 dozens of polaroids on High Resistivity Si 6, reflection through High Resistivity Si 6 and paraboloidal mirror is got on the electro-optic crystal ZnTe10, is loaded with the sample message THz wave conllinear of (comprising chromatic dispersion and absorption) on ZnTe crystal 10 with through 9 reflections of four paraboloidal mirrors and through sample 5.THz wave is surveyed light II by the electro-optic crystal modulation, thereby the information of sample is loaded on the detecting light beam.The detection light that is loaded with sample message finally is divided into two components that the polarization direction is vertical through quarter-wave plate 16 backs by Wollaston prism 11, at last modulate sample message by difference detecting by the difference of measuring two polarized components, thereby obtain the time waveform of terahertz pulse electric field.Time waveform is carried out the phase differential that Fourier transform obtains sample and object of reference, and be brought in the default computing formula, just can obtain the refractive index of sample.
Fig. 4 is the index of refraction diagram of photoresist in 0.2～2THz frequency range of the embodiment of the invention.
As shown in Figure 4, thickness is that the photoresist refractive index of 92 μ m and 146 μ m is consistent basically.The photoresist refractive index has slight fluctuation with the variation of frequency.But all in all, refractive index remains between 1.95～1.62 in 0.2～2THz frequency range.
In the present embodiment, the thickness of photoresist film is 92 μ m, and the refractive index of calculating at 0.56THz according to computing formula is 1.674.
Utilizability on the industry
The present invention can be widely used in fields such as optical measurement, optical instrument, optoelectronic device and biomedicine.
The effect of embodiment and effect
The assay method of photoresist refractive index according to the present invention, what the present invention measured is that photoresist is in the refractive index of terahertz electromagnetic wave, because photoresist is insensitive to terahertz electromagnetic wave, so photosensitized reaction can not take place, can realize accurately measuring the refractive index of exposure front and back photoresist in the Terahertz frequency range.
Embodiment two
In the present embodiment two, f is the frequency of terahertz electromagnetic wave, and occurrence can also be 0.2～2 THz.D is the thickness of photoresist film, and the thickness in the present embodiment can also be 146 μ m.If the thickness of photoresist film is 146 μ m, then the refractive index of calculating at 0.56THz according to computing formula is 1.670.Other step is just the same with embodiment one.
Claims (9)
1. the assay method of a photoresist refractive index is characterized in that, may further comprise the steps:
(1). photoresist liquid is dropped on the water surface, obtain photoresist film after solidifying, measure the thickness of described photoresist film;
(2). place the hollow bulb of back-shaped support and heating to obtain sample holder described photoresist film;
(3). use the terahertz time-domain spectroscopy system only to measure the time waveform of the impulse electric field of terahertz electromagnetic wave after by blank described back-shaped support, by obtaining phase place after the fourier transform and as with reference to phase place;
(4). the time waveform of the impulse electric field after using the described terahertz electromagnetic wave of terahertz time-domain spectroscopy system measurement by described sample holder, by obtaining phase place after the fourier transform and as the sample phase place;
(5). obtain phase differential according to described with reference to phase place and described sample phase place;
(6). obtain the refractive index of described photoresist in the Terahertz frequency range according to default computing formula;
Wherein, described computing formula is:
In described computing formula, n
sBe the refractive index of described photoresist in the Terahertz frequency range, n
rBe the refractive index of object of reference in the described back-shaped support of blank, described object of reference is air, n
rValue to be made as 1, c be terahertz electromagnetic wave velocity of propagation in a vacuum, occurrence is 3 * 10
8M/s, f are the frequency of terahertz electromagnetic wave, and occurrence is 0.1～10 THz, and d is the thickness of photoresist film, Δ φ be described with reference to phase place and described sample phase place the described phase differential in described Terahertz frequency range.
2. the assay method of photoresist refractive index according to claim 1, it is characterized in that: wherein, in the described step (1), described water is deionized water.
3. the assay method of photoresist refractive index according to claim 1, it is characterized in that: wherein, in the described step (1), the thickness of described photoresist film is 92 μ m and 146 μ m.
4. the assay method of photoresist refractive index according to claim 1, it is characterized in that: wherein, in the described step (1), the type of described photoresist is AZ 1500.
5. the assay method of photoresist refractive index according to claim 1, it is characterized in that: wherein, in the described step (1), service precision is the thickness that the electronic microcalliper of 0.001 mm is measured described photoresist film.
6. the assay method of photoresist refractive index according to claim 1, it is characterized in that: wherein, in the described step (2), described back-shaped support is aluminum products.
7. the assay method of photoresist refractive index according to claim 1, it is characterized in that: wherein, in described step (3) and the described step (4), the wavelength of the femtosecond pulse of described terahertz time-domain spectroscopy system is 800 nm, pulsewidth is 100 fs, and repetition frequency is 80 MHz.
8. the assay method of photoresist refractive index according to claim 1 is characterized in that: wherein, in the described step (5), described phase differential is the absolute value of described difference with reference to phase place and described sample phase place.
9. the assay method of photoresist refractive index according to claim 1, it is characterized in that: wherein, in the described step (6), the occurrence of the frequency of described terahertz electromagnetic wave is 0.2～2THz.
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| CN2013101226405A CN103196868A (en) | 2013-04-10 | 2013-04-10 | Determination method of refractive index of photoresist |
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| CN2013101226405A CN103196868A (en) | 2013-04-10 | 2013-04-10 | Determination method of refractive index of photoresist |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105300920A (en) * | 2015-06-29 | 2016-02-03 | 北京师范大学 | Method for extracting complex refractive index of solid sheet based on terahertz reflectance spectrum |
| CN105810841A (en) * | 2014-12-29 | 2016-07-27 | 固安翌光科技有限公司 | Organic electroluminescent device |
| CN107478604A (en) * | 2017-07-10 | 2017-12-15 | 中国科学院上海光学精密机械研究所 | The measurement apparatus and measuring method of refractive index of transparent materials |
| CN112255198A (en) * | 2020-10-19 | 2021-01-22 | 西安工程大学 | Method for detecting photosensitivity of substance |
| CN115165803A (en) * | 2022-09-08 | 2022-10-11 | 北京航空航天大学 | Device and method for measuring liquid refractive index |
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| CN102998725A (en) * | 2012-12-11 | 2013-03-27 | 电子科技大学 | Rough black metal film for absorbing terahertz radiation and preparation method of rough black metal film |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105810841A (en) * | 2014-12-29 | 2016-07-27 | 固安翌光科技有限公司 | Organic electroluminescent device |
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| CN107478604A (en) * | 2017-07-10 | 2017-12-15 | 中国科学院上海光学精密机械研究所 | The measurement apparatus and measuring method of refractive index of transparent materials |
| CN112255198A (en) * | 2020-10-19 | 2021-01-22 | 西安工程大学 | Method for detecting photosensitivity of substance |
| CN115165803A (en) * | 2022-09-08 | 2022-10-11 | 北京航空航天大学 | Device and method for measuring liquid refractive index |
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Inventor after: Zhang Dawei Inventor after: Wang Yinping Inventor after: Li Yuan Inventor after: Hong Ruijin Inventor after: Sheng Bin Inventor after: Huang Yuanshen Inventor after: Ni Zhengji Inventor after: Wang Qi Inventor before: Wang Yinping Inventor before: Zhang Dawei Inventor before: Li Yuan Inventor before: Hong Ruijin Inventor before: Sheng Bin Inventor before: Huang Yuanshen Inventor before: Ni Zhengji Inventor before: Wang Qi |
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Free format text: CORRECT: INVENTOR; FROM: WANG YINPING ZHANG DAWEI LI YUAN HONG RUIJIN SHENG BIN HUANG YUANSHEN NI ZHENGJI WANG QI TO: ZHANG DAWEI WANG YINPING LI YUAN HONG RUIJIN SHENG BIN HUANG YUANSHEN NI ZHENGJI WANG QI |
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Application publication date: 20130710 |