CN103018206B - Analyzing method of pollutant absorption capability of deep UV (ultraviolet) fluoride film element - Google Patents
Analyzing method of pollutant absorption capability of deep UV (ultraviolet) fluoride film element Download PDFInfo
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- CN103018206B CN103018206B CN201210532854.5A CN201210532854A CN103018206B CN 103018206 B CN103018206 B CN 103018206B CN 201210532854 A CN201210532854 A CN 201210532854A CN 103018206 B CN103018206 B CN 103018206B
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- fluoride film
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Abstract
The invention discloses an analyzing method of pollutant absorption capability of a deep UV (ultraviolet) fluoride film element, and belongs to the field of deep UV optics technology applications. The method comprises the following steps of: 1. testing the reflectivity R0 or transmittance T0 of a fluoride film sample after primary plating; 2. testing the reflectivity R1 or transmittance T1 after the sample absorbs organic matters or water vapor after the fluoride film sample is placed in an application environment system and is used or stored for a period of time; 3. carrying out low-power energy density irradiation on the surface of the sample by an ArF excimer laser, purging the dry high-purity N2 in the whole optical path system, and meanwhile monitoring the transmission laser energy by an energy meter; 4. carrying out spectrum testing on the sample after laser irradiation by the ArF excimer laser, thereby obtaining the reflectivity R2 or transmittance T2 of the sample after laser irradiation; and 5. operating an absorption factor Eta by the formula that Eta=Eta1+Eta2=(T2-T1)/T1+(T0-T2)/T0.
Description
Technical field
The present invention relates to a kind of analytical approach being applicable to deep ultraviolet fluoride film component contamination thing adsorptive power, belong to deep ultraviolet optical technical applications.
Background technology
The development pole the earth of integrated circuit technique has promoted the progress of human information society, become one of developing key core technology of Modern High-Tech, in national economy and social development, have very important significance, the research of deep ultraviolet optical correlation technique has great society and economic worth.In recent years, 193nm ArF excimer laser achieves widespread use as the light source of deep-UV lithography machine.The development of deep ultraviolet laser optical system and application requires to be proposed new challenge to deep ultraviolet optical film element function and long-time stability.
The root problem that deep ultraviolet optical film research faces is because deep ultraviolet wave band is near the forbidden band of most of dielectric material, makes to only have oxide Al
2o
3, SiO
2with partially fluorinated thing MgF
2, LaF
3, AlF
3etc. the needs that can meet the application of deep ultraviolet film.The limitation that membraneous material is selected brings the restriction to deep ultraviolet optical film preparation technology further, for fluoride, occur stoichiometric proportion mismatch for reducing deep ultraviolet optical film and cause absorption loss, thermal evaporation process is the optimal selection preparing fluoride film.Utilize hot boat Evaporation preparation technique, the deep ultraviolet fluoride optical thin film that can be absorbed less, but simultaneously also, the shortcoming such as Optical Coatings Surface more coarse fine and close not with optical thin film immanent structure.Therefore, deep ultraviolet optical film prepared by the hot boat evaporation technology of this employing, because optical thin film immanent structure is fine and close not and organic pollution materials in the more coarse adsorption applications environment that must bring of Optical Coatings Surface, make deep ultraviolet optical film performance degradation in use, this performance degradation causes thin-film component hydraulic performance decline even to lose efficacy, and this will cause catastrophic consequence to whole optical system.
Research shows, this deep ultraviolet optical film performance degradation concentrates on deep ultraviolet optical film inside and adsorption organic contaminant and steam and causes the absorption of deep ultraviolet optical film to enlarge markedly.Thus, analyzing the Performance Characteristics of adsorption fouling thing in deep ultraviolet thin-film component job applications environment, seeming particularly important for optimizing thin-film component preparation technology parameter optimization and thin-film component ambient adaptability and ageing assessment.
Summary of the invention
The present invention, in order to solve the problem of prior art, provides a kind of analytical approach of deep ultraviolet fluoride film component contamination thing adsorptive power.Accurate evaluation fluoride film sample is pollutant adsorptive power in applied environment or in storage environment, and then assessment different process or the thin-film component environmental suitability of different materials and ageing.There is provided reference for preparing the deep ultraviolet optical film with higher ambient adaptability, thus meet the needs that preparation has low stain, environmental stability good fluoride deep ultraviolet optical film element.
The analytical approach of deep ultraviolet fluoride film component contamination thing adsorptive power, comprises the following steps:
Step one: utilize vacuum spectrophotometer to purge dry high-purity N at whole cavity
2condition under, the test reflectivity R of fluoride film sample at the beginning of being coated with
0or transmitance T
0, as fluoride film sample spectra performance initial value;
Step 2: fluoride film sample uses or stores after a period of time being positioned in applied environment system, is positioned over by sample in vacuum spectrophotometer and carries out spectrum test in vacuum environment, obtain the reflectivity R after sample adsorption organism and steam
1or transmitance T
1;
Step 3: carry out low-power energy density irradiation to sample surfaces with ArF excimer laser, purges dry high-purity N in whole light path system
2, simultaneously with energy meter monitoring transmission laser energy;
Step 4: to the sample after the laser irradiation of ArF excimer laser, the same spectrum test described in carry out step one, obtains the reflectivity R of sample after laser irradiation
2or transmitance T
2;
Step 5: when test value is transmitance T, η=η
1+ η
2=(T
2-T
1)/T
1+ (T
0-T
2)/T
0, in formula, η is Sticking factor, η
1=(T
2-T
1)/T
1for element through ArF laser irradiation after stain thing adsorb can recovered part, η
2=(T
0-T
2)/T
0for the irrecoverable part that element adsorbs through ArF laser irradiation after stain thing, computing is carried out to the Sticking factor of sample in environment for use, and then thin-film component is assessed organic pollutant and Vapor adsorption ability in environment for use.
The present invention has following beneficial effect:
1, the method can the pollutant adsorptive power of complete effective assessment fluoride film sample in environment for use or storage environment, distinguish recoverable temporary transient absorbed portion and expendable permanent absorbed portion in sample adsorption pollutant by Ultra-Violet Laser radiation treatment, thus characterize the characterization of adsorption of fluoride film element comprehensively.
2, the method is equally applicable to the adsorptive power analysis of all fluoride monofilm materials, may be used for the adsorptive power of the fluoride film material dissecting deep ultraviolet wave band, as MgF
2, LaF
3, AlF
3, Na
3alF
6and GdF
3deng.
3, the method is applicable to all fluoride film material film elements that can be used for deep ultraviolet wave band, as antireflection film, high reverse--bias film and polarization film etc.
4, the method is applicable to distinguish fluoride materials of the same race thin-film component adsorption fouling thing ability under different thermal evaporation process parameter, for the improving and optimizating of technological parameter, prepares and has the adaptive deep ultraviolet optical film of higher environment and provide strong reference; This analytical approach can evaluate fluoride film element due to the Spectrum curve degradation performance that adsorption fouling thing causes in different environment for use simultaneously, thus meets the needs of fluoride film element ambient adaptability and ageing assessment.
Accompanying drawing explanation
Fig. 1 is the spectrum test figure that the pollutant adsorptive power analysis of deep ultraviolet fluoride antireflection film is carried out.
Embodiment
What occur in actual applications for deep ultraviolet fluoride optical thin film element is adsorbed with organic pollutants and steam, and then cause the problems such as Film Optics performance degradation, environment instability, need accurate analysis deep ultraviolet fluoride film element adsorption fouling thing ability characteristics in job applications environment or storage environment.By to causing the instable reason of deep ultraviolet fluoride optical thin film environment to be analyzed, and consider the test function of existing testing tool, the present invention utilizes the joint test of vacuum ultraviolet spectrophotometer spectrum test and ArF excimer laser surface irradiation process Real-Time Monitoring to assess, and discloses the analytical approach proposing a kind of deep ultraviolet wave band fluoride film element surface contaminant adsorptive power in applied environment.
Embodiment is as follows:
Step one: utilize vacuum spectrophotometer to purge dry high-purity N at whole cavity
2condition under, the test reflectivity R of fluoride film sample at the beginning of being coated with
0or transmitance T
0, as fluoride film sample spectra performance initial value.
Step 2: fluoride film sample uses or stores after a period of time being positioned in applied environment system, is positioned over by sample in vacuum spectrophotometer and carries out spectrum test in vacuum environment, obtain the spectral target reflectivity R after sample adsorption organism and steam
1or transmitance T
1.Being vacuum environment by spectrum test environmental selection, is to reduce because photometer test light is exactly ultraviolet light, can produce certain cleaning action impact to sample.In vacuum environment, organism is adsorbed in sample surfaces after decomposing under UV-irradiation again, and largely weakening spectrum test light affects the cleaning action of sample.If this test is at purging N
2carry out in environment, can along with N after organic substance decomposing
2discharge cavity, increase spectrum test light to the cleaning action of sample, cause the error of subsequent analysis result.
Step 3: low-power energy density (0.5-2mJ/cm is carried out to sample surfaces with ArF excimer laser
2) irradiation, purge dry high-purity N in whole light path system
2, so that pollutant discharges light path cavity smoothly, simultaneously with energy meter monitoring transmission laser energy, transmitted light intensity can constantly become large due to ArF laser to the cleaning function of the organic contaminant of sample surfaces, tends towards stability after a period of time.
Step 4: to the sample after the laser irradiation of ArF excimer laser, carries out the same spectrum test as described in step one, obtains the reflectivity R of sample after laser irradiation
2or transmitance T
2.
Step 5: in order to the performance of fluorine analysis compound thin-film component adsorb organic compound in environment for use, when test value is transmitance T, η=η
1+ η
2=(T
2-T
1)/T
1+ (T
0-T
2)/T
0, in formula, η is Sticking factor, η
1=(T
2-T
1)/T
1for element through ArF laser irradiation after stain thing adsorb can recovered part, namely represent ' temporarily ' characterization of adsorption of sample, η
2=(T
0-T
2)/T
0for the irrecoverable part that element adsorbs through ArF laser irradiation after stain thing, namely represent ' forever ' characterization of adsorption of sample.By carrying out related operation to the Sticking factor of sample in environment for use, and then thin-film component is assessed organic pollutant and Vapor adsorption ability in environment for use.
Testing tool used in the present invention comprises vacuum ultraviolet spectrophotometer and ArF excimer laser.Wherein vacuum ultraviolet spectrophotometer can (P<10 in a vacuum
-6mbar) or purge N
2carry out transmitance and absolute reflectance test in (99.999%) two kind of environment, measuring accuracy is 0.5%, and testing light source range of choice is 115-300nm.ArF excimer laser frequency 1kHz, energy density 0.5-50mJ/cm
2.
Embodiment 1
The present embodiment carries out organic pollutant in standard laboratory atmosphere (temperature 22 DEG C, relative humidity 30%) for the fluoride antireflection film under a kind of hot boat Evaporation preparation technological parameter and Vapor adsorption ability is assessed.
As shown in Figure 1, for the laboratory environment organic contaminant of deep ultraviolet fluoride antireflection film of the present invention and Vapor adsorption ability carry out spectrum test evaluation graph.
After being coated with comprising this fluoride antireflection film, spectrophotometer is in purging high-purity N
2time test transmitance at 193nm wave band transmitance T
0be 98.4% as this antireflection film sample spectra performance initial value.
This thin-film component is placed in laboratory environment after 2 weeks, spectrophotometer is at vacuum environment (P<10
-6mbar) transmitance of this sample is tested at 193nm wave band transmitance T
1become 97.6%, visible sample reduces about 0.8%, simultaneously because the suction-operated of thin-film component causes operation wavelength ' blue shift ' about 1nm due to the spectral target transmitance after adsorb organic compound and steam.
With ArF excimer laser, 1mJ/cm is carried out to sample surfaces
2low-power energy density irradiation, purges dry high-purity N in whole light path system
2, so that pollutant discharges light path cavity smoothly, simultaneously with energy meter monitoring transmission laser energy, transmitted light intensity can constantly become large due to ArF laser to the cleaning function of the organic contaminant of sample surfaces, approximately experiences 10
5tend towards stability after individual laser pulse, stop laser irradiation.
With ultraviolet vacuum spectrophotometer, purging high-purity N is carried out to the sample after laser irradiation
2spectral transmittance test under environment, obtains the transmitance of this sample at the T of 193nm wave band transmitance by predose
1=97.6% brings up to T
2=98.2%.According to the formula η=(T described in such as step 5
2-T
1)/T
1+ (T
0-T
2)/T
0obtaining the Sticking factor of this film sample under standard laboratory atmosphere condition is 0.815%, wherein can recover absorbed portion, ' temporarily ' absorption η
1account for 0.615%, ' forever ' absorption η
2account for 0.200%.Visible, by this kind of method, can the characterization of adsorption of this thin-film component of comprehensive characterization under standard laboratory atmosphere condition.
By the adsorptive power analytical approach of organism and steam in the fluoride film element application environment described in the present invention, rational evaluation fluoride film can be evaluated in the environment to organic pollutant adsorptive power, to preparation have the thin-film component of environmental stability process optimization, evaluate thin-film component ambient adaptability and ageing effective.
Claims (2)
1. the analytical approach of deep ultraviolet fluoride film component contamination thing adsorptive power, is characterized in that, comprise the following steps:
Step one: utilize vacuum spectrophotometer to purge dry high-purity N at whole cavity
2condition under, the test reflectivity R of fluoride film sample at the beginning of being coated with
0or transmitance T
0, as fluoride film sample spectra performance initial value;
Step 2: fluoride film sample uses or stores after a period of time being positioned in applied environment system, is positioned over by sample in vacuum spectrophotometer and carries out spectrum test in vacuum environment, obtain the spectral target reflectivity R after sample adsorption organism and steam
1or transmitance T
1;
Step 3: carry out low-power energy density irradiation to sample surfaces with ArF excimer laser, purges dry high-purity N in whole light path system
2, simultaneously with energy meter monitoring transmission laser energy;
Step 4: to the sample after the laser irradiation of ArF excimer laser, the same test described in also carry out step one, obtains the reflectivity R of sample after laser irradiation
2or transmitance T
2;
Step 5: when test value is transmitance T, η=η
1+ η
2=(T
2-T
1)/T
1+ (T
0-T
2)/T
0, in formula, η is Sticking factor, η
1=(T
2-T
1)/T
1for element through ArF laser irradiation after stain thing adsorb can recovered part, η
2=(T
0-T
2)/T
0for the irrecoverable part that element adsorbs through ArF laser irradiation after stain thing, computing is carried out to the Sticking factor η of sample in environment for use, and then thin-film component is assessed organic pollutant and Vapor adsorption ability in environment for use.
2. the analytical approach of deep ultraviolet fluoride film component contamination thing adsorptive power according to claim 1, it is characterized in that, the power energy density described in step 3 is 0.5-2mJ/cm
2.
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|---|---|---|---|
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| CN103018206B true CN103018206B (en) | 2014-12-24 |
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