TWI432320B - 封裝膜、封裝結構與其形成方法 - Google Patents
封裝膜、封裝結構與其形成方法 Download PDFInfo
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- TWI432320B TWI432320B TW099140309A TW99140309A TWI432320B TW I432320 B TWI432320 B TW I432320B TW 099140309 A TW099140309 A TW 099140309A TW 99140309 A TW99140309 A TW 99140309A TW I432320 B TWI432320 B TW I432320B
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- hydrophilic group
- monomer
- inorganic oxide
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- 238000000034 method Methods 0.000 title claims description 17
- 238000005538 encapsulation Methods 0.000 title description 13
- 239000010410 layer Substances 0.000 claims description 70
- 239000000178 monomer Substances 0.000 claims description 31
- 229910052809 inorganic oxide Inorganic materials 0.000 claims description 28
- 239000004372 Polyvinyl alcohol Substances 0.000 claims description 18
- 229920002451 polyvinyl alcohol Polymers 0.000 claims description 18
- 238000000231 atomic layer deposition Methods 0.000 claims description 17
- 125000002887 hydroxy group Chemical group [H]O* 0.000 claims description 13
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 12
- 229920000642 polymer Polymers 0.000 claims description 8
- MCMNRKCIXSYSNV-UHFFFAOYSA-N Zirconium dioxide Chemical compound O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 claims description 6
- 125000002843 carboxylic acid group Chemical group 0.000 claims description 3
- 238000000576 coating method Methods 0.000 claims description 3
- 239000011248 coating agent Substances 0.000 claims description 2
- 239000012044 organic layer Substances 0.000 claims 12
- 238000006243 chemical reaction Methods 0.000 description 13
- 229920001577 copolymer Polymers 0.000 description 11
- 239000007789 gas Substances 0.000 description 11
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 11
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 description 10
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 description 10
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 description 8
- 230000035699 permeability Effects 0.000 description 8
- 239000000758 substrate Substances 0.000 description 7
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 6
- JLTRXTDYQLMHGR-UHFFFAOYSA-N trimethylaluminium Chemical compound C[Al](C)C JLTRXTDYQLMHGR-UHFFFAOYSA-N 0.000 description 6
- 229920002554 vinyl polymer Polymers 0.000 description 6
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 4
- 239000001307 helium Substances 0.000 description 4
- 229910052734 helium Inorganic materials 0.000 description 4
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 4
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 4
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 229910052786 argon Inorganic materials 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 239000005038 ethylene vinyl acetate Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 230000035515 penetration Effects 0.000 description 3
- 229920001200 poly(ethylene-vinyl acetate) Polymers 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-N Dimethylamine Chemical compound CNC ROSDSFDQCJNGOL-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 2
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 2
- 239000006227 byproduct Substances 0.000 description 2
- 238000000151 deposition Methods 0.000 description 2
- 230000008021 deposition Effects 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 239000011261 inert gas Substances 0.000 description 2
- 238000005259 measurement Methods 0.000 description 2
- 229910052757 nitrogen Inorganic materials 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 229920002037 poly(vinyl butyral) polymer Polymers 0.000 description 2
- 229920002338 polyhydroxyethylmethacrylate Polymers 0.000 description 2
- 238000002834 transmittance Methods 0.000 description 2
- CBECDWUDYQOTSW-UHFFFAOYSA-N 2-ethylbut-3-enal Chemical compound CCC(C=C)C=O CBECDWUDYQOTSW-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 description 1
- 239000004642 Polyimide Substances 0.000 description 1
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 1
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical compound ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007334 copolymerization reaction Methods 0.000 description 1
- 210000005069 ears Anatomy 0.000 description 1
- -1 ethylene, propylene, butene Chemical class 0.000 description 1
- 238000009459 flexible packaging Methods 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 229910000449 hafnium oxide Inorganic materials 0.000 description 1
- WIHZLLGSGQNAGK-UHFFFAOYSA-N hafnium(4+);oxygen(2-) Chemical compound [O-2].[O-2].[Hf+4] WIHZLLGSGQNAGK-UHFFFAOYSA-N 0.000 description 1
- 150000003949 imides Chemical class 0.000 description 1
- 239000004973 liquid crystal related substance Substances 0.000 description 1
- JTHNLKXLWOXOQK-UHFFFAOYSA-N n-propyl vinyl ketone Natural products CCCC(=O)C=C JTHNLKXLWOXOQK-UHFFFAOYSA-N 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000012299 nitrogen atmosphere Substances 0.000 description 1
- 230000006911 nucleation Effects 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 229920000620 organic polymer Polymers 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 150000002923 oximes Chemical class 0.000 description 1
- SIWVEOZUMHYXCS-UHFFFAOYSA-N oxo(oxoyttriooxy)yttrium Chemical compound O=[Y]O[Y]=O SIWVEOZUMHYXCS-UHFFFAOYSA-N 0.000 description 1
- BPUBBGLMJRNUCC-UHFFFAOYSA-N oxygen(2-);tantalum(5+) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[Ta+5].[Ta+5] BPUBBGLMJRNUCC-UHFFFAOYSA-N 0.000 description 1
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 1
- 239000012785 packaging film Substances 0.000 description 1
- 229920006280 packaging film Polymers 0.000 description 1
- 239000005022 packaging material Substances 0.000 description 1
- NFHFRUOZVGFOOS-UHFFFAOYSA-N palladium;triphenylphosphane Chemical compound [Pd].C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1.C1=CC=CC=C1P(C=1C=CC=CC=1)C1=CC=CC=C1 NFHFRUOZVGFOOS-UHFFFAOYSA-N 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 239000004033 plastic Substances 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920001721 polyimide Polymers 0.000 description 1
- 230000000379 polymerizing effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 230000010349 pulsation Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229920005989 resin Polymers 0.000 description 1
- 239000011347 resin Substances 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 229910001936 tantalum oxide Inorganic materials 0.000 description 1
- 238000004383 yellowing Methods 0.000 description 1
- RUDFQVOCFDJEEF-UHFFFAOYSA-N yttrium(III) oxide Inorganic materials [O-2].[O-2].[O-2].[Y+3].[Y+3] RUDFQVOCFDJEEF-UHFFFAOYSA-N 0.000 description 1
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910001928 zirconium oxide Inorganic materials 0.000 description 1
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F8/00—Chemical modification by after-treatment
- C08F8/42—Introducing metal atoms or metal-containing groups
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/04—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof adapted as photovoltaic [PV] conversion devices
- H01L31/042—PV modules or arrays of single PV cells
- H01L31/048—Encapsulation of modules
- H01L31/0481—Encapsulation of modules characterised by the composition of the encapsulation material
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L33/00—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L33/48—Semiconductor devices having potential barriers specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor body packages
- H01L33/52—Encapsulations
- H01L33/56—Materials, e.g. epoxy or silicone resin
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E10/00—Energy generation through renewable energy sources
- Y02E10/50—Photovoltaic [PV] energy
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- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Organic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Microelectronics & Electronic Packaging (AREA)
- Condensed Matter Physics & Semiconductors (AREA)
- General Physics & Mathematics (AREA)
- Engineering & Computer Science (AREA)
- Physics & Mathematics (AREA)
- Power Engineering (AREA)
- Electromagnetism (AREA)
- Computer Hardware Design (AREA)
- Laminated Bodies (AREA)
- Chemical Vapour Deposition (AREA)
- Electroluminescent Light Sources (AREA)
- Photovoltaic Devices (AREA)
Description
本發明係關於一種封裝結構,更特別關於其採用之封裝膜。
目前商用太陽電池模組多使用耐濕性佳之乙烯-醋酸乙烯酯共聚物(EVA)作為封裝材料。不過EVA等羰基樹脂在太陽光之紫外線照射下容易損壞變黃,進而影響太陽光的穿透效率。目前的取代方案之一為紫外線穿透效率高的乙烯醇縮丁醛-乙烯醇-醋酸乙烯酯共聚物(poly(vinyl butryl-co-vinyl alcohol-co-vinyl acetate)。然而上述共聚物的羥基容易吸水,無法避免水氣損害其封裝的太陽電池。綜上所述,目前亟需降低上述含羥基之共聚物的吸水性,使其應用於太陽電池等光電元件中。
本發明提供一種封裝膜,包括含親水基之聚合物所形成的有機封裝層;以及無機氧化物層,形成於有機封裝層上;其中無機氧化物層與有機封裝層之間具有共價鍵結。
本發明亦提供一種封裝結構,包括光電元件;以及上述之封裝膜包覆光電元件;其中有機封裝層係夾設於光電元件與無機氧化物層之間。
本發明更提供一種封裝結構之形成方法,包括提供光電元件;以含親水基之聚合物所形成的有機封裝層包覆光電元件;以及以原子層沉積法形成無機氧化物層於有機封裝層上,其中無機氧化物層與有機封裝層之間具有共價鍵結。
本發明提供一種封裝結構之形成方法。如第1圖之封裝結構所示,提供基板10上的光電元件11。基板10為可撓性材質如塑膠。光電元件可為將電能轉換為光能的裝置如發光二極體(LED)或液晶顯示器(LCD),亦可為將光能轉換為電能的裝置如太陽能電池。接著以含親水基之單體聚合而成的有機聚合物作為有機封裝層13,以包覆光電元件11,其中該有機封裝層13形成後,其表面仍具有親水性官能基,例如聚乙烯醇(Polyvinyl alcohol,PVA)、聚丙烯酸(Polyacrylate)、聚乙烯醇縮丁醛(Polyvinyl butyral,PVB)、聚甲基丙烯酸羥乙酯(poly hydroxyethyl methacrylate,pHEMA)。在本發明一實施例中,親水基係羥基或羧酸基,而有機封裝層13可為聚乙烯醇(PVA)。在本發明另一實施例中,可進一步採用其他不含親水基之單體與上述親水基之單體共聚形成有機封裝層13,但含親水基之單體與不含親水基之單體的莫耳比例大於50:50。若含親水基之單體的莫耳比例小於不含親水基之單體的莫耳比例,則無法有助於原子層沈積薄膜成核成長。形成聚合物後仍具有親水基之單體例如乙烯醇(vinyl alcohol)、乙烯醇缩丁醛(vinyl butyral)或甲基丙烯酸羥乙酯(hydroxyethyl methacrylate,HEMA);而形成聚合物後不具有親水基之單體例如乙烯(ethylene)、丙烯(propylene)、丁烯(butene)、氯乙烯(vinyl chloride)、異戊二烯(isoprene)、苯乙烯(styrene)、醯亞胺(imide)、甲基丙烯酸甲酯(MMA)、醋酸乙烯酯(vinyl acetate)。舉例來說,有機封裝層13可為聚乙烯醇(PVA)、乙烯醇縮丁醛-乙烯醇-醋酸乙烯酯共聚物、或甲基丙烯酸羥乙酯(HEMA)與甲基丙烯酸甲酯(MMA)共聚物,其中以HEMA和MMA的共聚物中包括的含之親水基的單體(HEMA)與不含親水基的單體(MMA)的莫耳比例大於50:50者為佳。以有機封裝層13封裝光電元件11的方法可為塗佈法。在本發明一實施例中,有機封裝層13之厚度介於1μm-20μm之間。若有機封裝層13的厚度過薄,將無法有效覆蓋基板,並影響後續有機封裝層薄膜之成長品質。若有機封裝層13的厚度過厚,將造成透光度下降。
接著以原子層沉積法形成無機氧化物層15於有機封裝層13上。上述之原子層沉積法為低溫製程,其溫度約介於50至120℃之間。若原子層沉積法的溫度過低,則無機氧化層之成長時間過久。若原子層沉積法的溫度過高,則可能損傷有機封裝層13,甚至損傷有機封裝層13包覆之光電元件11。原子層沉積法的原理是利用前驅物氣體或加熱後的蒸氣產生的脈動,在欲沉積的基材表面逐層成長的薄膜。舉例來說,可先利用氬氣將三甲基鋁加熱後的蒸氣送入反應腔室中。藉由三甲基鋁與有機封裝層13表面的羥基反應如式1。在式1中,n為有機封裝層13表面的羥基數目。
有機封裝層表面-(OH)n
+nAl(CH3
)3
→有機封裝層表面-(O-Al(CH3
)2
*)n
+nCH4
(式1)
接著以Ar或N2
等無反應性氣體淨化反應腔室,清除多餘的三甲基鋁及反應的副產物甲烷。接著將氧化源的H2
O導入反應腔,進行式2的反應。
有機封裝層表面-(O-Al(CH3
)2
*)n
+2nH2
O→有機封裝層表面-(O-Al-(OH)2
*)n
+2nCH4
(式2)
接著再以Ar或N2
等無反應性氣體淨化反應腔室,清除多餘的水氣與副產物甲烷。上述式1-2的反應與兩個清潔步驟稱為一個ALD循環,其表面將再一次佈滿羥基。上述循環可不斷重複,直到成長足夠厚度之無機氧化物層15。由上述說明可知,有機封裝層13的表面與無機氧化層15之間具有共價鍵結。上述之無機氧化物層15可為單層材料如氧化鋁、氧化鋅、氧化鋯、氧化矽、或氧化鉿,亦可為交替排列之多層材料如氧化鋁/氧化鋯。在本發明一實施例中,無機氧化物層15之厚度介於5nm至100nm之間。若無機氧化物層15之厚度過薄,則無法有效阻擋水氣或其他污染物損害光電元件11。若無機氧化物層之厚度過厚,則會降低封裝結構之透光性及可撓性。由於無機氧化物層15為緻密的奈米級結構,並不會影響有機封裝層13之可撓性質。換句話說,由無機氧化物層15與有機封裝層13組成的封裝膜為可撓性。若基板10與光電元件11亦具有可撓性,再搭配上述的可撓式封裝膜,將可完成可撓的封裝結構。
為了讓本發明之上述和其他目的、特徵、和優點能更明顯易懂,下文特舉數實施例配合所附圖式,作詳細說明如下:
【實施例】
水氣穿透率實驗
使用MOCON公司生產之MOCON Aquatran量測。
氦氣穿透實驗
使用Helium Leakage detector量測。
氧氣穿透實驗
使用MOCON公司生產之MOCON Oxtran量測。
實施例1
取市售之乙烯醇縮丁醛-乙烯醇-醋酸乙烯酯共聚物薄膜(Polyvinyl butyral-vinyl alcohol-vinyl acetate,購自長春化工),於50℃下進行原子層沉積法以沉積氧化鋁層於共聚物薄膜上,步驟如下:
a.在一原子層沉積裝置(購自Cambridge NanoTech公司)內,將前述之共聚物薄膜置入反應腔室中,通入三甲基鋁氣體,在120℃之下進行沉積反應,氣體pulse時間為0.03秒鐘;
b.通入Ar氣體抽氣時間5秒鐘;
c.通入加熱溫度至25℃之水蒸氣,pulse時間0.02秒;
d.通入Ar氣體抽氣時間5秒鐘;
反覆循環進行a.至d.步驟70次;
得到的氧化鋁層,其厚度約為35 nm。
實施例2
取市售之之聚乙烯醇(PVA)薄膜(購自長春化工),其結構如下方式1所示。接著於120℃下進行原子層沉積法同實施例1,以沉積氧化鋁層於聚乙烯醇薄膜上,其氧化鋁厚度約為35 nm。
實施例3
取市售之聚乙烯醇(PVA)薄膜(購自長春化工)。接著於120℃下進行原子層沉積法,並交替沉積氧化鋁層(2)/氧化鉿層(3)於聚乙烯醇薄膜上,步驟如下:
a.在一原子層沉積裝置(購自Cambridge NanoTech公司)內,將前述之聚乙烯醇薄膜置入反應腔室中,通入三甲基鋁氣體,在溫度120℃之下進行沉積反應,pulse時間0.03秒鐘;
b.通入Ar氣體抽氣時間5秒鐘;
c.通入加熱溫度至25℃之水蒸氣,pulse時間為0.02秒鐘;
d.通入Ar氣體抽氣時間5秒鐘;
e.重複a.步驟,唯僅將三甲基鋁改以四(二甲基胺)鉿,並接續進行b.至d.步驟;
反覆進行a.至e.步驟70次;
得到的多層氧化物厚度約為35 nm。
實施例4
取甲基丙烯酸羥乙酯(2-Hydroxyethyl 2-methylprop-2-enoate,簡稱HEMA,其結構如下方式2所示)與甲基丙烯酸甲酯(methyl 2-methylpropenoate,簡稱MMA,其結構如下方式3所示)共聚所形成之共聚物薄膜,此薄膜之合成方法例如將6莫耳的HEMA單體與4莫耳的MMA單體共同溶解於甲醇中,置於氮氣環境之下,加入自由基起始劑AIBN(Azobisisobutyronitrile) 80毫克,以水浴加熱至65℃並保持水平震盪速度400 rpm,反應24小時,單體之進料方式可直接同時進入反應槽內,進料比例是以控制單體莫耳比例的方式進行,以本實施例而言,HEMA單體與MMA單體之莫耳比例係大於50:50。接著同實施例1,於120℃下進行原子層沉積法以沉積氧化鋁層於HEMA共聚物薄膜上。得到的氧化鋁厚度約為35 nm。
比較例1
取聚醯亞胺(Polyimide,PI,其結構如下方式4所示)薄膜,其單體不具有羥基。接著同實施例1,於120℃下進行原子層沉積法以沉積氧化鋁層於PI薄膜上。得到的氧化鋁厚度約為35 nm。
固定四種實施例與一種比較例之無機氧化物厚度,其水氣穿透率、氧氣穿透率、及氦氣穿透率結果比較如表1所示。
由表1可知,ALD成長之氧化鋁層可大幅降低含羥基單體之共聚物的水氣穿透率。而具有更多羥基之PVA的水氣穿透率會大於乙烯醇縮丁醛-乙烯醇-醋酸乙烯酯共聚物。此外,由實施例1、2、4與比較例1對照可知,隨著共聚高分子中具有親水基的單體與不含親水基的單體的莫耳比例增加,其氦氣穿透率隨之減少,亦即阻氣能力提高,這是因為更多的羥基可讓原子層沉積之氧化鋁與薄膜表面之間的共價鍵密度更高,可進一步的降低複合膜的水氣穿透率。綜上所述,一般認為不適於封裝光電元件的高吸水性PVA在搭配ALD沉積之氧化鋁後,反而比含有少量羥基之共聚物更適於作為封裝膜。此外,當採用交替的的氧化鋁/氧化鉿之多層結構時,其水氣、氧氣、及氦氣之穿透率會比類似厚度之單一氧化鋁層低。
雖然本發明已以數個較佳實施例揭露如上,然其並非用以限定本發明,任何熟習此技藝者,在不脫離本發明之精神和範圍內,當可作任意之更動與潤飾,因此本發明之保護範圍當視後附之申請專利範圍所界定者為準。
10...基板
11...光電元件
13...有機封裝層
15...無機氧化物層
第1圖係本發明一實施例之封裝結構的示意圖。
10...基板
11...光電元件
13...有機封裝層
15...無機氧化物層
Claims (10)
- 一種封裝膜,包括:一含親水基之聚合物所形成的一有機層;以及一無機氧化物層,形成於該有機層上;其中該無機氧化物層與該有機層之間具有共價鍵結,其中該親水基係羥基或羧酸基,且該無機氧化物層係交替排列之氧化鋁與氧化鋯。
- 如申請專利範圍第1項所述之封裝膜,其中該有機層包括聚乙烯醇。
- 如申請專利範圍第1項所述之封裝膜,其中該有機層更包括一由不含親水基之單體與含親水基之單體所共聚形成者,且該含親水基之單體與該不含親水基之單體的莫耳比例大於50:50。
- 如申請專利範圍第1項所述之封裝膜,其中該無機氧化物層之厚度介於5nm至100nm之間。
- 一種封裝結構,包括:一光電元件;以及如申請專利範圍第1項所述之封裝膜包覆該光電元件;其中該有機層係夾設於該光電元件與該無機氧化物層之間。
- 一種封裝結構之形成方法,包括:提供一光電元件;以一含親水基之聚合物所形成的一有機層包覆該光電元件;以及以原子層沉積法形成一無機氧化物層於該有機層上, 其中該無機氧化物層與該有機層之間具有共價鍵結,其中該親水基係羥基或羧酸基,且該無機氧化物層係交替排列之氧化鋁與氧化鋯。
- 如申請專利範圍第6項所述之封裝結構之形成方法,其中該有機層包括聚乙烯醇。
- 如申請專利範圍第6項所述之封裝結構之形成方法,其中,該含親水基之聚合物係以不含親水基之單體與含親水基之單體共聚形成該有機層,且該含親水基之單體與該不含親水基之單體的莫耳比例大於50:50。
- 如申請專利範圍第6項所述之封裝結構之形成方法,其中該無機氧化物層之厚度介於5nm至100nm之間。
- 如申請專利範圍第6項所述之封裝結構之形成方法,其中以原子層沉積法形成該無機氧化物層於該有機層上的溫度介於25至120℃之間。
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