光電材料暨檢測研討會 分子光譜 於光電材料上的應用 2009 Perkin Elmer Tiffany Kang 康瑜容 Tiffany.Kang@perkinelmer.com PerkinElmer Taiwan 珀金埃爾默股份有限公司 什麼是分子光譜? Increasing Wavelength 50,000 12,820 4000 400 cm-1 Gamma X-ray UV NIR IR FIR Micro Radio 200 380 780 2500 25 000 nm Increasing Energy K 層電子外層電子分子振動分子轉動 UVS-2 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 1
分子光譜的組成 分光光譜儀主要元件 : 燈源 : 陶瓷燈源 氙燈 鎢鹵燈 氘燈 雷射.. 光學元件 : 稜鏡 光柵 干涉儀.. 偵測器 DTGS MCT P t di d PMT 偵測器 :DTGS MCT Potodiode PMT. 使用分光光譜儀目的在於對化合物之定性定量 Beer s Law A=εbC 分光光譜儀使用上優點 : 樣品無需前處理 不破壞樣品 分析時間快速 + + Detector UVS-3 Part (I) 平面顯示器相關材料 2009 Perkin Elmer PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 2
光電產業光譜量測的需求 LCD 產業的量測需求 ITO 穿透率 (%T) 及反射率 (%R) 背光膜 反射率 (%R) 彩色濾光片 穿透率 (%T) 及 CIE 參數 Polarize filter 穿透率 (%T) 及極化率 (Polarization Factor) 5 最新的 UV/Vis & UV/Vis/NIR 光譜量測設備介紹 光譜儀主體 紫外光 / 可見光分光光譜儀 Lambda 650 Wavelength : 190~900nm UV/Vis resolution : 0.17nm Lambda 850 Wavelength : 175~900nm UV/Vis resolution : 0.05nm 紫外光 / 可見光 / 近紅外光分光光譜儀 Lambda 950 Wavelength : 175~3300nm UV/Vis resolution : 0.05nm NIR resolution : 0.20nm 6 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 3
Inside the Lambda Series 7 8 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 4
光譜量測技術介紹 配件部分 2009 Perkin Elmer When the incident light thought a material UVS-10 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 5
穿透附件 單一入射角 可變入射角 (manual type) 0~60 degree 0~360 degree 可變入射角 (Auto type) Defined by user S 0~360 degree rotation stage Light 量測樣品種類 : color filter, polarize filter, ITO glass Polarize need or not??? UVS-11 Solution 1 color filter analysis (any filter) Transmittance holder Result text PerkinElmer Lambda 650/850/950 Color software Color method spectrum Result graph UVS-12 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 6
Polarize light?? 量測 Polarize filter 時 量測穿透及反射入射角大於 10 度時 光源在經偏極化前需為 random light (depolarize light) 0~360 degree UVS-13 Solution 2 Polarize filter 單體 / 偏光片組量測 CBDepolarizer Polarizer Driver & holder Lambda 650/850/950 Sample holder color Software 偏光片 1 偏光片 2 自動尋找直交及平行所對應的角度 測量偏光片在不同入射角度下的穿透率 (0~360 degree) 自動計算極化率 P = 14 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 7
配向膜 配向膜是控制 LCD 顯示品質的關鍵材料, 用於液晶顯示器上下電極基板的內側, 目的在控制液晶分子排列方向 0~360 degree 0~360 degree 15 Solution 3 配向膜 CBDepolarizer Polarizer Driver & Sample holder 配向膜錨定能量測 Lambda 650/850/950 Rotation Stage Software 偏光片 1 樣品 偏光片 2 自動定位 cross 角度及樣品與光軸垂直 轉動偏光片 2, 找到光通過的最小角度為 θ1 轉動樣品 φ 角 (user defined) 轉動偏光片 2, 找到光通過的最小角度為 θ2 16 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 8
Solution 4 Test Cell ASSP Rotation Stage & Function Generator Test Cell & 視角特性量測 Lambda 650/850/950 Sample holder Software 波形產生器 樣品槽 偏光片 + 彩色率光片 + 液晶 +TFT 量測不同入射角及不同輸入電壓下的穿透圖譜 計算色度座標值 XYZ, Lab, Yxy 17 Solution 5 ITO glass ASSP Software Fiber stage Common Beam Depolarizer Lambda 650/850/950 Sphere detector Fiber Stage ITO glass 18 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 9
反射模式量測 鏡面反射 (specular reflectance) AR (Anti Reflectance) HR (High Reflectance) 2009 Perkin Elmer Specular Reflectance- 相對反射附件 (1) 單一固定角度 : near normal angle 6,45,80 degree 6 degree 45 degree 20 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 10
Specular Reflectance- 相對反射附件 (2) 可變角度 : 15 to 70 degree 21 Specular Reflectance- 絕對反射附件 (1) 單一固定角度 (AR / HR) VN type: near normal angle 8,15,30,45,60 degree 22 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 11
Specular Reflectance- 絕對反射附件 (2) 單一固定角度 (HR) VW type: near normal angle 7.5 23 VW variable angle absolute Accessory (3) VW accessory shown with polarizer installed Laser alignment makes setup quick and easy +/- 8~80 degree, 0.1 degree setting 24 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 12
New URA accessory (4) 8 to 70 degree Full automatic 25 26 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 13
散射模式量測 散射反射 (diffuse reflectance) 2009 Perkin Elmer Integrating Sphere - 積分球 60mm Integrating Sphere Spectralon coating inside PMT & PbS detector Reflectance ( 8 degree incident angle) Transmittance 0 degree incident angle Yindex measurement Reference port (front) 穿透樣品座 反射樣品座 Reference port (back) 28 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 14
150MM SPHERE Haze 150 mm Diffuse Reflectance Integrating Sphere Center Mount Clip and Jaw Style Small Spot Kit 29 Part (II) 太陽能相關材料 2009 Perkin Elmer PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 15
Solar Energy 的利用 太陽能的應用 Broad categories of solar energy applications 儲能裝置 Energy Conservation 建築玻璃 Architectural glass 產能裝置 Energy Production 聚光用途 Solar concentrators 太陽能電池 ( 光伏 ) Photovoltaics 光熱收集器 Solar Thermal Collectors UVS-31 Photovoltaics Cell UVS-32 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 16
Photovoltaic Cell UVS-33 What a UV/VIS/NIR Spectrometer for? Measure 穿透 Transmission Total or Diffuse Transmission 反射 Reflectance Specular Reflectance Total or Diffuse Reflectance 吸收 Absorbance UVS-34 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 17
為何使用積分球附件? 2009 Perkin Elmer Some Causes of Sampling Error Poor parallelism Rough surface Poor surface finish Internal cloudiness Internal distortion Thick samples UVS-36 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 18
Integrating Spheres What Type of Samples? Glass Coatings Filters Powders Paints Plastics Semiconductor Optics Crystals Precious stones Sunglasses Scattering liquids Cosmetics Architectural Glass Automotive Glass Inks Paper Thin Film Coated Glass Liquid crystals Ceramics Clothing Contact lenses UVS-37 What type of measurements? %T Diffuse %T Variable Angle %T Absorptance %R Diffuse %R Specular %R Total %R Haze Opacity CIE Color Solar Direct Transmittance Solar Direct Reflectance Solar Direct Absorptance Light Transmittance (Solar) Light Reflectance (Solar) UV Transmittance (Solar) UVA, UVB Thin Film Thickness S and P Polarization i UVS-38 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 19
穿透的量測 Transmittance Measurements 直線穿透 Normal Transmittance 散射穿透 Diffuse Transmittance UVS-39 Integrating Sphere Transmission Measurements Simplified diagram of an Integrating Sphere Accessory. Note reference beam path not shown. UVS-40 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 20
Typical Method Transmittance Measurements Transmission spectra of two different glass bottle bottoms, showing different levels of UVA and UVB light protection. UVS-41 反射量測 Specular and Diffuse Reflectance Illustration of Specular and Diffuse Reflectance UVS-42 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 21
Specular and Diffuse Reflectance Both Diffuse and Total Reflectance can be measured directly with an integrating sphere 散射反射 Diffuse Reflectance measurements require that the specular light component be excluded 全反射 Total Reflectance measurements require that the specular light component be included 鏡面反射 Specular Reflectance can be indirectly determined by subtracting the diffuse component spectrum from the total component spectrum. UVS-43 Diffuse Reflectance Diffuse reflectance is measured on an integrating sphere by placing the sample at the reflectance port (8 ) with the specular port in an open position UVS-44 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 22
Total Reflectance Total reflectance is measured on an integrating sphere by placing the sample at the reflectance port (8 ) with the specular port in the closed position UVS-45 鏡面反射 Specular Reflectance 的計算 Specular Reflectance Measurements Total and Diffuse %R Curves Specular %R Curve Specular Reflectance Calculation with the PELA 1000 of a pink colored ceramic tile. The measured total reflectance spectrum minus the diffuse spectrum yields the specular reflectance of the sample. UVS-46 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 23
吸收的量測 Absorbance Measurements 吸收值 Absorbance: The percentage of energy incident on a specimen that is not directly transmitted or reflected. When light impinges i on a clear solid, part of the light is reflected, part is transmitted, and part is absorbed by the material. This expression is often described as T + R + A = 1 %Absorbance = 100% Direct Transmission %Reflected Absorbance is indirectly measured with an integrating sphere by obtaining the %R and %T spectra of the specimen. The absorbance is then calculated from the two spectra. UVS-47 吸收的計算 Typical Application Absorptance Measurements Absorptance Calculation from %R and %T Spectra of PVC Exterior Covering using the Advanced Spectroscopy Software Package UVS-48 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 24
Solar Cell measured with Integrating Sphere The application was to characterize a silicon photocell wafer The overlaid spectra shows the hemispherical reflectance and transmittance of the wafer at 8 incidence (reflectance) and normal incidence (transmittance) over the solar range from 200 nm 1300 nm. With a highly scattering sample such as a silicon wafer, an integrating i sphere is necessary to measure the scattered transmittance. UVS-49 Solar Cell measured with the Center Mount 同時量測 Transmittance 及 Reflectance The graphic shows the change in absorption of a solar cell at 10, 20, 30, 40, 50, and 60 incidence angles with hemispherical collection. Using the optional clip style center mount for the 150 mm Integrating Sphere. The graphic shows the measurement in absorption (AP = 1 T R). We have now the possibility to calculate the thickness of any coating over the silicon. The coating can be either a protective film or an anti reflecting coating. UVS-50 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 25
Solar Glass Solar glass 的特性 Low iron glass (presence of iron makes glass green) 高穿透 high sunlight transmission eg. super white solar glass 低反射 low reflectivity to the sunlight Solar glass are used as the cover glass panel of PV cell and solarpowered water heaters Solar glass 的厚度 將會影響可見光 visible range (380 780 nm) 穿透度 同時會影響熱性質 thermal conductivity i and emissivity i i of the glass Good transmittance through solar glass of solar module UVS-51 Patterned Solar Glass Trapping of Light Some solar glass are just plain, some have a sandy smooth texture and some even prismatically patterned to promote adhesion as well as to allow higher transmission at acute incident angles. Besides transmission, reflection and haze measurement the glass become important as well. Clear Hazy External reflection at a glass surface (n=1.52) showing s and p polarized components UVS-52 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 26
Solar Glass Light Trapping with Anti Reflection Coating External reflection at a glass surface (n=1.52) showing s and p polarized components Representation of a single layer anti reflection coating Reproduced from Melles Griot 1998 Single layer MgF2 anti reflection coating UVS-53 Antireflective coating effects on different wavelengths 7.00 Anti reflection coating on glass 6.0 5.0 %R 4.0 3.0 2.0 1.0 0.00 600.0 700 800 900 1000 1100 1200 1300 1400 1500 1600.0 nm UVS-54 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 27
Integrating Sphere Thin Films Measurements Transmission spectrum of front surface of alloy coated thin film solar glass Reflection spectrum of surface of alloy coated solar glass surface Reflection spectrum of uncoated glass side of alloy coated solar glass surface Transmission and reflection measurements are useful for quality control and specification UVS-55 霧度量測 Haze Measurement Haze Procedure based on ASTM 1003 92 Standard Method for Haze and Luminous Transmittance of Transparent Plastics 用以了解有多少 Diffuse transmittance 的比例 Haze = [(T4/T2) (T3/T1)] x 100% where Measurement Position A Position B T1 No Specimen White Standard T2 Specimen White Standard T3 No Specimen Light Trap T4 Specimen Light Trap Patterned solar glass UVS-56 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 28
Integrating Sphere Haze Measurements UVS-57 Haze Calculations UVS-58 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 29
100.0 %T 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 100.0 %T 15 10 0.0 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 300.0 400 500 600 700 800 900 1000 1100 1200 1300 1400 1500 1600 1700 1800 1900 2000.0 nm 5 0-6.8 300.0 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720 740 760 780 800.0 nm 100.0 %T 95 90 85 80 75 70 65 60 55 50 45 40 35 30 25 20 15 10 5 0-6.8 300.0 320 340 360 380 400 420 440 460 480 500 520 540 560 580 600 620 640 660 680 700 720 740 760 780 800.0 nm Integrating Sphere Optical Transmission Haze Measurements of Polysilicon Coated Solar Glass Sample 1-1 Transmission of smooth front surface of solar glass sample F-1 Transmission of smooth front surface of solar glass sample F-2 Haze = [(T4/T2) (T3/T1)] x 100% F-1 Haze measurement F-2 Haze measurement T2 T2 Polysilicon coated solar glass Polysilicon coated solar glass T4 T4 T3 T3 Sample Haze % F 1 9.10 F 2 21.24 Illuminant:A Haze calculations are especially useful for quality control and specification purposes UVS-59 Measuring the Solar Transmission and Reflectance of Materials 太陽光穿透特性 Solar absorbance Solar reflectance Solar transmittance 將太陽光的頻譜加權計算 The solar transmittance, reflectance, or absorbance is determined by calculating a weighted average with a standard solar irradiance 波長範圍 Measurements of spectral near normal hemispherical transmittance (or reflectance) are made over the spectral range from 300 to 2500 nm. UVS-60 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 30
Solar measurements Architectural Glass Recent developments in coating techniques have allowed builders to use glass as a material which h participates i t actively in heating and cooling control. Efficient window design incorporates coated glass in a double or triple pane configuration. The transmission of visible light, total solar energy and longer wave thermal radiation can be controlled within wide limits to reduce energy consumption for the regulation of temperature in a building. UVS-61 UV/VIS/NIR Spectra of Architectural Glass 100 90 VISIBLE (LIGHT) NEAR INFRARED (HEAT) 80 %T 70 60 50 40 30 20 10 UV The energy distribution within the solar spectrum is approximately 2% UV, 47% visible, and 51% infrared. Over 50% of the total solar energy that reaches Earth is in the near infrared portion of the energy spectrum 0 200 400 600 800 1000 1200 1400 1600 1800 2000 2200 2500 Uncoated glass UV protection coat nm Low E coat, moderate solar gain Low solar gain coat UVS-62 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 31
Ratings for Architectural Glass National Fenestration Rating Council (NFRC.org) U factor: Indicates the rate of total heat transfer through a window and its frame (without sunlight). Solar heat gain coefficient (SHGC): Derived from a solar weighted spectrum of UV/VIS/NIR light transmitted through a window. Visible transmittance (VT): The amount of VIS light transmitted. These items are rated on a scale of 0 to 1. UVS-63 ASTM, EN, and ISO Methodologies for Solar Measurements ASTM E 903 96 Standard Test method for Solar Absorptance, Reflectance, and Transmittance of Materials using Integrating Spheres ASTM E 424 71 ASTM E 490 73 ASTM E 891 87 ISO 9050 / EN 410 Standard Test Method for Transmittance and Reflectance (Terrestrial) of Sheet Materials Standard Solar Constant and Air Mass Zero Solar Spectral Irradiance Tables Standard Tables for Terrestrial Direct Normal Solar Spectral Irradiance for Air Mass 1.5 Glass in building - Determination of light transmittance, solar direct transmittance, total solar energy, transmittance and ultraviolet transmittance, and related glazing factors. UVS-64 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 32
Solar Spectral Curve UV VIS NIR UVS-65 Description of Air Mass AMx AM0 The Air Mass number is the distance of the sunlight through the atmosphere longer than the vertical distance. Sunlight passing through the atmosphere is absorbed by water vapor and carbon dioxide as well as scattered by the atmosphere. AM1 is of lower intensity and has absorption bands compared to AM0 AM1,5 AM1 ATMOSPHERE EARTH UVS-66 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 33
Architectural Glass Calculations Normal, Double, Triple Glazing Light Transmission Light Reflectance Light Absorptance Solar Transmission Solar Reflectance Solar Absorptance Solar Factor / Glazing Factor UV Transmission UVA Transmission UVB Transmission Color Rendering (Ra) Solar Output per unit area (Os) Solar Response (Rs) Convolution UVS-67 Architectural Glass Calculations Solar Distributions Global Global 2 Global 3 P. Moon Air Mass 1.5 D65 Solar Solar 2 UV User definable Unlimited number UV / IR Correction Thickness Compensation Result Templates Automation UVS-68 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 34
Solar Table for Air Mass 2 Relative spectral distribution of direct solar radiation S according to P.Moon for air mass 2 multiplied by the spectral bandwidth UVS-69 Solar Measurements Architectural Glass Coated Low E Glass helps prevent heat from escaping in the winter, and helps prevent heat from entering in the summer. UVS-70 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 35
Solar Measurements Architectural Glass Reflectance, Transmittance, and Absorptance of solar energy on double paned, air insulated architectural glass. UVS-71 Architectural Glass Diagram of a double pane window Low E coating Reflects long wave thermal radiation, affects the U factor. Solar control coating Reflects or absorbs solar radiation, allowing visible light to be transmitted. The coating design and its placement in the window structure can be adjusted to achieve the desired effect. UVS-72 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 36
Solar Measurements Architectural Glass Example Performance Data for Architectural Glass UVS-73 Architectural Glass Calculation Window UVS-74 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 37
Solar Reflectance Vinyl Siding Materials T 1 UVS-75 Solar Reflectance Vinyl Siding Materials UVS-76 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 38
Solar Reflectance Vinyl Siding Materials ASTM Test Method E903 (1996) Method Name : AM150g.mgx Analyst : Method Info.: Date: 02 Mar 04 Time : 03:53 PM Type: AM 1.5 W Wavelength Range: 305.00 nm to 2494.00 nm % Reflectance Specimen Code UV Vis NIR Solar 2_573527.SP 7.66 25.76 51.14 37.32 2_573528.SP 6.67 19.77 51.09 34.26 2_573557.SP 10.62 47.23 69.36 56.79 2_573560.SP 10.45 47.97 72.51 58.64 2_573556.SP 10.18 56.12 71.23 62.12 2_573559.SP 10.57 58.46 75.99 65.56 UVS-77 New Solar Products Light Management and Power Generation New developments in glass products which combine light management and power generation. The technology allows glass windows to produce electricity via solar energy while allowing light to pass through. PV cells can also be integrated into walls and tiles as part of the buildings or applied as films on surfaces solar panel with a unique semitransparent finish used as a skylight integrated roof photovoltaic system designed to form a complete roof UVS-78 PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 39
太陽能電池 PV Cell Properties Measurement 2009 Perkin Elmer Band Gap and the Photovoltaic Effect Conductor Semiconductor Insulator Conduction Band Band Gap ev Valence Band The band gap refers to the energy needed to move an electron from its ground state in the valence band to the conduction band. PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 40
Band gap and the photovoltaic effect Two or more very thin layers of semiconductor or conductor material can be stacked to produce a PV cell. _ + n p Light absorbed near the p n junction creates voltage potential The incident photons must have energy equal to or slightly greater than the band gap energy for the absorbing material. Transmission spectrum of Silicon Thin crystalline Silicon 60.0 55 50 45 %T 40 35 30 25 20 15 10 5 Free carrier absorption 0.0 190.0 400 600 800 1000 1200 1400 1600 1800 2000 2200 2400 2600.0 nm 1.1 ev PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 41
Energy Conservation & Renewable Energy Research Developing technologies Solar technologies are of major interest Billions of dollars are being spent on research, worldwide Silicon no longer the only source Thin films are being developed to reduce cost New manufacturing techniques to lower cost Improvements in efficiencies is a major current driver Weathering of the materials is an important consideration Transmission spectrum of CdTe Thin film of CdTe on glass 1.5 ev PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 42
Triple Junction Solar Cell Design Material Symb Band gap (ev) Silicon Si 1.11 Germanium Ge 0.67 Aluminum phosphide AlP 2.45 Gallium(III) phosphide GaP 2.26 Gallium(III) arsenide GaAs 1.43 Gallium(III) nitride GaN 3.4 Gallium antimonide GaSb 0.7 Indium(III) phosphide InP 1.35 Indium(III) arsenide InAs 0.36 Substrate 1.9 ev 1.4 ev 1.1 ev Three different materials allow absorption over a broad wavelength range. Multi layer thin films Multiple layers of thin films can produce very complex interference patterns. Multilayer thin films Substrate PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 43
Aluminium reflective coatings. Construction of reflective material FilmStar Film Thickness Calculator l Visible spectra of component layers Softwares such as FilmStar can help to do design and analysis of optical thin films of these multilayers. Visit www.ftgsoftware.com. have a multilayer composition Q and A Thank you very much PerkinElmer Taiwan 珀金埃爾默 ( 股 ) 公司 44