US20150155506A1 - Method of preparing molybdenum oxide films - Google Patents
Method of preparing molybdenum oxide films Download PDFInfo
- Publication number
- US20150155506A1 US20150155506A1 US14/618,404 US201514618404A US2015155506A1 US 20150155506 A1 US20150155506 A1 US 20150155506A1 US 201514618404 A US201514618404 A US 201514618404A US 2015155506 A1 US2015155506 A1 US 2015155506A1
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- United States
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- film
- moo
- ink
- substrate
- coating
- Prior art date
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- Abandoned
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- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910000476 molybdenum oxide Inorganic materials 0.000 title abstract description 14
- PQQKPALAQIIWST-UHFFFAOYSA-N oxomolybdenum Chemical compound [Mo]=O PQQKPALAQIIWST-UHFFFAOYSA-N 0.000 title abstract description 14
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000758 substrate Substances 0.000 claims abstract description 34
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 32
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 30
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 30
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 30
- 229910017053 inorganic salt Inorganic materials 0.000 claims abstract description 17
- 239000002904 solvent Substances 0.000 claims abstract description 12
- 239000011877 solvent mixture Substances 0.000 claims abstract description 6
- 239000011248 coating agent Substances 0.000 claims description 15
- 238000000576 coating method Methods 0.000 claims description 15
- 239000011521 glass Substances 0.000 claims description 10
- 238000000137 annealing Methods 0.000 claims description 6
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical group [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 4
- 238000007639 printing Methods 0.000 claims description 4
- 238000004528 spin coating Methods 0.000 claims description 4
- 238000010345 tape casting Methods 0.000 claims description 4
- 238000007641 inkjet printing Methods 0.000 claims description 3
- 239000002985 plastic film Substances 0.000 claims description 3
- 229920006255 plastic film Polymers 0.000 claims description 3
- 238000007764 slot die coating Methods 0.000 claims description 3
- 239000004642 Polyimide Substances 0.000 claims description 2
- 238000007766 curtain coating Methods 0.000 claims description 2
- 238000007646 gravure printing Methods 0.000 claims description 2
- 238000007645 offset printing Methods 0.000 claims description 2
- 238000007649 pad printing Methods 0.000 claims description 2
- 229920001721 polyimide Polymers 0.000 claims description 2
- 238000007650 screen-printing Methods 0.000 claims description 2
- 238000005507 spraying Methods 0.000 claims description 2
- 239000000976 ink Substances 0.000 abstract description 57
- 230000005693 optoelectronics Effects 0.000 abstract description 20
- 239000010408 film Substances 0.000 description 65
- 239000010410 layer Substances 0.000 description 43
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 38
- 238000013086 organic photovoltaic Methods 0.000 description 37
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 19
- 239000011592 zinc chloride Substances 0.000 description 19
- 229920000144 PEDOT:PSS Polymers 0.000 description 17
- 239000000654 additive Substances 0.000 description 17
- 229910000041 hydrogen chloride Inorganic materials 0.000 description 17
- IXCSERBJSXMMFS-UHFFFAOYSA-N hydrogen chloride Substances Cl.Cl IXCSERBJSXMMFS-UHFFFAOYSA-N 0.000 description 17
- -1 poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 14
- 230000000996 additive effect Effects 0.000 description 11
- MCEWYIDBDVPMES-UHFFFAOYSA-N [60]pcbm Chemical compound C123C(C4=C5C6=C7C8=C9C%10=C%11C%12=C%13C%14=C%15C%16=C%17C%18=C(C=%19C=%20C%18=C%18C%16=C%13C%13=C%11C9=C9C7=C(C=%20C9=C%13%18)C(C7=%19)=C96)C6=C%11C%17=C%15C%13=C%15C%14=C%12C%12=C%10C%10=C85)=C9C7=C6C2=C%11C%13=C2C%15=C%12C%10=C4C23C1(CCCC(=O)OC)C1=CC=CC=C1 MCEWYIDBDVPMES-UHFFFAOYSA-N 0.000 description 10
- 229920000301 poly(3-hexylthiophene-2,5-diyl) polymer Polymers 0.000 description 10
- 235000002639 sodium chloride Nutrition 0.000 description 9
- UXVMQQNJUSDDNG-UHFFFAOYSA-L Calcium chloride Chemical compound [Cl-].[Cl-].[Ca+2] UXVMQQNJUSDDNG-UHFFFAOYSA-L 0.000 description 8
- 239000001110 calcium chloride Substances 0.000 description 8
- 229910001628 calcium chloride Inorganic materials 0.000 description 8
- 238000002156 mixing Methods 0.000 description 8
- 229920000642 polymer Polymers 0.000 description 8
- 229910019626 (NH4)6Mo7O24 Inorganic materials 0.000 description 7
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 7
- GNTDGMZSJNCJKK-UHFFFAOYSA-N divanadium pentaoxide Chemical compound O=[V](=O)O[V](=O)=O GNTDGMZSJNCJKK-UHFFFAOYSA-N 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 5
- 239000002253 acid Substances 0.000 description 5
- 239000000203 mixture Substances 0.000 description 5
- 238000002360 preparation method Methods 0.000 description 5
- 239000010409 thin film Substances 0.000 description 5
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 5
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 4
- CPELXLSAUQHCOX-UHFFFAOYSA-N Hydrogen bromide Chemical compound Br CPELXLSAUQHCOX-UHFFFAOYSA-N 0.000 description 4
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 4
- 230000008901 benefit Effects 0.000 description 4
- 229910001850 copernicium Inorganic materials 0.000 description 4
- LELOWRISYMNNSU-UHFFFAOYSA-N hydrogen cyanide Chemical compound N#C LELOWRISYMNNSU-UHFFFAOYSA-N 0.000 description 4
- XMBWDFGMSWQBCA-UHFFFAOYSA-N hydrogen iodide Chemical compound I XMBWDFGMSWQBCA-UHFFFAOYSA-N 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- VLTRZXGMWDSKGL-UHFFFAOYSA-N perchloric acid Chemical compound OCl(=O)(=O)=O VLTRZXGMWDSKGL-UHFFFAOYSA-N 0.000 description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 description 4
- 230000008569 process Effects 0.000 description 4
- 235000005074 zinc chloride Nutrition 0.000 description 4
- RFFLAFLAYFXFSW-UHFFFAOYSA-N 1,2-dichlorobenzene Chemical compound ClC1=CC=CC=C1Cl RFFLAFLAYFXFSW-UHFFFAOYSA-N 0.000 description 3
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 description 3
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 230000006872 improvement Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910001507 metal halide Inorganic materials 0.000 description 3
- 150000005309 metal halides Chemical group 0.000 description 3
- 229910044991 metal oxide Inorganic materials 0.000 description 3
- 150000004706 metal oxides Chemical group 0.000 description 3
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification Methods 0.000 description 3
- 238000005457 optimization Methods 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 2
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 2
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N Dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 description 2
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 description 2
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 2
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 description 2
- LSNNMFCWUKXFEE-UHFFFAOYSA-N Sulfurous acid Chemical compound OS(O)=O LSNNMFCWUKXFEE-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 238000004630 atomic force microscopy Methods 0.000 description 2
- LWBPNIJBHRISSS-UHFFFAOYSA-L beryllium dichloride Chemical compound Cl[Be]Cl LWBPNIJBHRISSS-UHFFFAOYSA-L 0.000 description 2
- KGBXLFKZBHKPEV-UHFFFAOYSA-N boric acid Chemical compound OB(O)O KGBXLFKZBHKPEV-UHFFFAOYSA-N 0.000 description 2
- 239000004327 boric acid Substances 0.000 description 2
- KPWJBEFBFLRCLH-UHFFFAOYSA-L cadmium bromide Chemical compound Br[Cd]Br KPWJBEFBFLRCLH-UHFFFAOYSA-L 0.000 description 2
- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 description 2
- OKIIEJOIXGHUKX-UHFFFAOYSA-L cadmium iodide Chemical compound [Cd+2].[I-].[I-] OKIIEJOIXGHUKX-UHFFFAOYSA-L 0.000 description 2
- XTEGARKTQYYJKE-UHFFFAOYSA-N chloric acid Chemical compound OCl(=O)=O XTEGARKTQYYJKE-UHFFFAOYSA-N 0.000 description 2
- 229940005991 chloric acid Drugs 0.000 description 2
- QBWCMBCROVPCKQ-UHFFFAOYSA-N chlorous acid Chemical compound OCl=O QBWCMBCROVPCKQ-UHFFFAOYSA-N 0.000 description 2
- 229940077239 chlorous acid Drugs 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000014509 gene expression Effects 0.000 description 2
- 229910000042 hydrogen bromide Inorganic materials 0.000 description 2
- 229910000043 hydrogen iodide Inorganic materials 0.000 description 2
- 238000011835 investigation Methods 0.000 description 2
- 239000003446 ligand Substances 0.000 description 2
- 239000008204 material by function Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 229910017604 nitric acid Inorganic materials 0.000 description 2
- 229940074355 nitric acid Drugs 0.000 description 2
- ACVYVLVWPXVTIT-UHFFFAOYSA-N phosphinic acid Chemical compound O[PH2]=O ACVYVLVWPXVTIT-UHFFFAOYSA-N 0.000 description 2
- 229940032330 sulfuric acid Drugs 0.000 description 2
- 238000002207 thermal evaporation Methods 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten(VI) oxide Inorganic materials O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- VNDYJBBGRKZCSX-UHFFFAOYSA-L zinc bromide Chemical compound Br[Zn]Br VNDYJBBGRKZCSX-UHFFFAOYSA-L 0.000 description 2
- UAYWVJHJZHQCIE-UHFFFAOYSA-L zinc iodide Chemical compound I[Zn]I UAYWVJHJZHQCIE-UHFFFAOYSA-L 0.000 description 2
- 229910019934 (NH4)2MoO4 Inorganic materials 0.000 description 1
- XMWRBQBLMFGWIX-UHFFFAOYSA-N C60 fullerene Chemical class C12=C3C(C4=C56)=C7C8=C5C5=C9C%10=C6C6=C4C1=C1C4=C6C6=C%10C%10=C9C9=C%11C5=C8C5=C8C7=C3C3=C7C2=C1C1=C2C4=C6C4=C%10C6=C9C9=C%11C5=C5C8=C3C3=C7C1=C1C2=C4C6=C2C9=C5C3=C12 XMWRBQBLMFGWIX-UHFFFAOYSA-N 0.000 description 1
- OYPRJOBELJOOCE-UHFFFAOYSA-N Calcium Chemical compound [Ca] OYPRJOBELJOOCE-UHFFFAOYSA-N 0.000 description 1
- UNMYWSMUMWPJLR-UHFFFAOYSA-L Calcium iodide Chemical compound [Ca+2].[I-].[I-] UNMYWSMUMWPJLR-UHFFFAOYSA-L 0.000 description 1
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-M Fluoride anion Chemical compound [F-] KRHYYFGTRYWZRS-UHFFFAOYSA-M 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- CBENFWSGALASAD-UHFFFAOYSA-N Ozone Chemical compound [O-][O+]=O CBENFWSGALASAD-UHFFFAOYSA-N 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- VIUODKCIIYIXHC-UHFFFAOYSA-L [I-].[I-].[Ra+2] Chemical compound [I-].[I-].[Ra+2] VIUODKCIIYIXHC-UHFFFAOYSA-L 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001298 alcohols Chemical class 0.000 description 1
- 239000004411 aluminium Substances 0.000 description 1
- 229910052782 aluminium Inorganic materials 0.000 description 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 1
- QGAVSDVURUSLQK-UHFFFAOYSA-N ammonium heptamolybdate Chemical compound N.N.N.N.N.N.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.O.[Mo].[Mo].[Mo].[Mo].[Mo].[Mo].[Mo] QGAVSDVURUSLQK-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000000089 atomic force micrograph Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- XUFUCDNVOXXQQC-UHFFFAOYSA-L azane;hydroxy-(hydroxy(dioxo)molybdenio)oxy-dioxomolybdenum Chemical compound N.N.O[Mo](=O)(=O)O[Mo](O)(=O)=O XUFUCDNVOXXQQC-UHFFFAOYSA-L 0.000 description 1
- 229910052788 barium Inorganic materials 0.000 description 1
- DSAJWYNOEDNPEQ-UHFFFAOYSA-N barium atom Chemical compound [Ba] DSAJWYNOEDNPEQ-UHFFFAOYSA-N 0.000 description 1
- NKQIMNKPSDEDMO-UHFFFAOYSA-L barium bromide Chemical compound [Br-].[Br-].[Ba+2] NKQIMNKPSDEDMO-UHFFFAOYSA-L 0.000 description 1
- 229910001620 barium bromide Inorganic materials 0.000 description 1
- WDIHJSXYQDMJHN-UHFFFAOYSA-L barium chloride Chemical compound [Cl-].[Cl-].[Ba+2] WDIHJSXYQDMJHN-UHFFFAOYSA-L 0.000 description 1
- 229910001626 barium chloride Inorganic materials 0.000 description 1
- SGUXGJPBTNFBAD-UHFFFAOYSA-L barium iodide Chemical compound [I-].[I-].[Ba+2] SGUXGJPBTNFBAD-UHFFFAOYSA-L 0.000 description 1
- 229910001638 barium iodide Inorganic materials 0.000 description 1
- 229940075444 barium iodide Drugs 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- OVHDZBAFUMEXCX-UHFFFAOYSA-N benzyl 4-methylbenzenesulfonate Chemical compound C1=CC(C)=CC=C1S(=O)(=O)OCC1=CC=CC=C1 OVHDZBAFUMEXCX-UHFFFAOYSA-N 0.000 description 1
- 229910052790 beryllium Inorganic materials 0.000 description 1
- ATBAMAFKBVZNFJ-UHFFFAOYSA-N beryllium atom Chemical compound [Be] ATBAMAFKBVZNFJ-UHFFFAOYSA-N 0.000 description 1
- 229910001621 beryllium bromide Inorganic materials 0.000 description 1
- PBKYCFJFZMEFRS-UHFFFAOYSA-L beryllium bromide Chemical compound [Be+2].[Br-].[Br-] PBKYCFJFZMEFRS-UHFFFAOYSA-L 0.000 description 1
- 229910001627 beryllium chloride Inorganic materials 0.000 description 1
- 229910001639 beryllium iodide Inorganic materials 0.000 description 1
- JUCWKFHIHJQTFR-UHFFFAOYSA-L beryllium iodide Chemical compound [Be+2].[I-].[I-] JUCWKFHIHJQTFR-UHFFFAOYSA-L 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229920001400 block copolymer Polymers 0.000 description 1
- 229910052793 cadmium Inorganic materials 0.000 description 1
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 1
- 229940075417 cadmium iodide Drugs 0.000 description 1
- 239000011575 calcium Substances 0.000 description 1
- 229910052791 calcium Inorganic materials 0.000 description 1
- 229910001622 calcium bromide Inorganic materials 0.000 description 1
- WGEFECGEFUFIQW-UHFFFAOYSA-L calcium dibromide Chemical compound [Ca+2].[Br-].[Br-] WGEFECGEFUFIQW-UHFFFAOYSA-L 0.000 description 1
- 229910001640 calcium iodide Inorganic materials 0.000 description 1
- 229940046413 calcium iodide Drugs 0.000 description 1
- 125000002915 carbonyl group Chemical group [*:2]C([*:1])=O 0.000 description 1
- 230000008859 change Effects 0.000 description 1
- RCTYPNKXASFOBE-UHFFFAOYSA-M chloromercury Chemical compound [Hg]Cl RCTYPNKXASFOBE-UHFFFAOYSA-M 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 229920000547 conjugated polymer Polymers 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 230000003028 elevating effect Effects 0.000 description 1
- 238000000572 ellipsometry Methods 0.000 description 1
- 150000002148 esters Chemical class 0.000 description 1
- 238000001704 evaporation Methods 0.000 description 1
- 230000008020 evaporation Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 238000009472 formulation Methods 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 229910010272 inorganic material Inorganic materials 0.000 description 1
- 239000011147 inorganic material Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- OTCKOJUMXQWKQG-UHFFFAOYSA-L magnesium bromide Chemical compound [Mg+2].[Br-].[Br-] OTCKOJUMXQWKQG-UHFFFAOYSA-L 0.000 description 1
- 229910001623 magnesium bromide Inorganic materials 0.000 description 1
- 229910001629 magnesium chloride Inorganic materials 0.000 description 1
- BLQJIBCZHWBKSL-UHFFFAOYSA-L magnesium iodide Chemical compound [Mg+2].[I-].[I-] BLQJIBCZHWBKSL-UHFFFAOYSA-L 0.000 description 1
- 229910001641 magnesium iodide Inorganic materials 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- NGYIMTKLQULBOO-UHFFFAOYSA-L mercury dibromide Chemical compound Br[Hg]Br NGYIMTKLQULBOO-UHFFFAOYSA-L 0.000 description 1
- QKEOZZYXWAIQFO-UHFFFAOYSA-M mercury(1+);iodide Chemical compound [Hg]I QKEOZZYXWAIQFO-UHFFFAOYSA-M 0.000 description 1
- 239000005078 molybdenum compound Substances 0.000 description 1
- 150000002752 molybdenum compounds Chemical class 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 239000012044 organic layer Substances 0.000 description 1
- 239000011368 organic material Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 238000009832 plasma treatment Methods 0.000 description 1
- 239000002798 polar solvent Substances 0.000 description 1
- 239000013047 polymeric layer Substances 0.000 description 1
- 229920000123 polythiophene Polymers 0.000 description 1
- 229910052705 radium Inorganic materials 0.000 description 1
- HCWPIIXVSYCSAN-UHFFFAOYSA-N radium atom Chemical compound [Ra] HCWPIIXVSYCSAN-UHFFFAOYSA-N 0.000 description 1
- GIKWXTHTIQCTIH-UHFFFAOYSA-L radium bromide Chemical compound [Br-].[Br-].[Ra+2] GIKWXTHTIQCTIH-UHFFFAOYSA-L 0.000 description 1
- 229910001624 radium bromide Inorganic materials 0.000 description 1
- 229940075451 radium bromide Drugs 0.000 description 1
- RWRDJVNMSZYMDV-UHFFFAOYSA-L radium chloride Chemical compound [Cl-].[Cl-].[Ra+2] RWRDJVNMSZYMDV-UHFFFAOYSA-L 0.000 description 1
- 229910001630 radium chloride Inorganic materials 0.000 description 1
- 229910001642 radium iodide Inorganic materials 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 150000003384 small molecules Chemical class 0.000 description 1
- 229910052712 strontium Inorganic materials 0.000 description 1
- CIOAGBVUUVVLOB-UHFFFAOYSA-N strontium atom Chemical compound [Sr] CIOAGBVUUVVLOB-UHFFFAOYSA-N 0.000 description 1
- YJPVTCSBVRMESK-UHFFFAOYSA-L strontium bromide Chemical compound [Br-].[Br-].[Sr+2] YJPVTCSBVRMESK-UHFFFAOYSA-L 0.000 description 1
- 229910001625 strontium bromide Inorganic materials 0.000 description 1
- 229940074155 strontium bromide Drugs 0.000 description 1
- 229910001631 strontium chloride Inorganic materials 0.000 description 1
- AHBGXTDRMVNFER-UHFFFAOYSA-L strontium dichloride Chemical compound [Cl-].[Cl-].[Sr+2] AHBGXTDRMVNFER-UHFFFAOYSA-L 0.000 description 1
- KRIJWFBRWPCESA-UHFFFAOYSA-L strontium iodide Chemical compound [Sr+2].[I-].[I-] KRIJWFBRWPCESA-UHFFFAOYSA-L 0.000 description 1
- 229910001643 strontium iodide Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 239000000725 suspension Substances 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 229910001428 transition metal ion Inorganic materials 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229940102001 zinc bromide Drugs 0.000 description 1
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- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09D—COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR
- C09D11/00—Inks
- C09D11/52—Electrically conductive inks
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- H01L51/422—
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Abstract
Present invention relates to methods of preparing molybdenum oxide inks and molybdenum oxide films, and use of the molybdenum oxide films as hole-transporting layers in optoelectronic devices. The ink for forming a hybrid molybdenum (VI) oxide (MoO3) film on a substrate comprises an ammonium molybdate, at least one inorganic salt different from ammonium molybdate, and a solvent or a solvent mixture.
Description
- This application claims the benefit of priority of Singapore Patent Application No. 201203804-8, filed May 24, 2012, the contents of which being hereby incorporated by reference in its entirety for all purposes.
- The invention relates to methods of preparing molybdenum oxide inks and molybdenum oxide films, and use of the molybdenum oxide films as hole-transporting layers in optoelectronic devices.
- Organic photovoltaic (OPV) cells have seen remarkable progress in the past few decades. OPV devices using a bulk heterojunction (BHJ) based photoactive layer, positioned between an electron-donating semiconducting polymer and an electron-accepting fullerene derivative, are one of the most promising systems in this field. The most well-investigated BHJ based polymer solar cells consists of poly (3-hexylthiophene) and [6,6]-phenyl C61-butyric acid methyl ester (P3HT:PCBM) blend with a power conversion efficiency (PCE) of 5%. In polymer solar cell technology, chemical tailoring allows an endless possibility of engineering a semiconducting polymer with appropriate absorption and charge transport properties. In the last few years, there are varieties of novel low band gap semiconducting polymers, such as 2,7-carbazole based copolymers, and polythiophene derivatives, as an electron donor have been developed for solar cell applications with an aim to enhance the PCE. As a result, the efficiency of polymer solar cells has been steadily improving, with PCE breaking the 9% barrier.
- Recent advancements in most OPV technology relies on poly(3,4-ethylenedioxythiophene):poly(styrene sulfonate) (PEDOT:PSS) as the hole-transporting layer. It is commonly adopted as the anode buffer layer in traditional polymer OPV cells due to its high transparency, high work function, smooth morphology and good conductivity. However, there are several disadvantages in using PEDOT:PSS as the hole-transporting layer, particularly with regard to its moisture permeability. As a film, PEDOT:PSS consists of doped conjugated polymer chains. The polymer grains are defined by PSS random coils with PEDOT chains attached. The area between the grains comprises of excess PSS. It has been suggested that the excess PSS can diffuse into the polymeric/organic layer, which will then possibly undergo a chemical reaction, which is undesirable.
- In order to circumvent this, PEDOT:PSS has been replaced with metal oxides such as molybdenum (VI) oxide (MoO3), vanadium (V) oxide (V2O5), and tungsten (VI) oxide (WO3). The replacement of PEDOT:PSS was also mooted in order to improve the charge extraction by improving the built-in potential, hence elevating the overall PCE.
- Most attempts to deposit MoO3 were performed via thermal evaporation means. This will be impractical for all solution-processable materials systems for large area electronics and optoelectronics devices. Furthermore, thermal evaporation involves the use of a vacuum chamber, which consumes lots of energy. Since simple large-scale processing is one of the prerequisites for practical large area production application, solution-processed MoO3 is a much more favorable proposition. Solution processability allows the use of methods such as spin-coating, slot die coating, inkjet printing, roll-to-roll manufacturing, for example.
- Recently, a method for solution processable MoO3 films spin-coated from a nanoparticle suspension for organic electronics is developed. The MoO3 nanoparticles were pre-prepared and suspended with an undisclosed block copolymer. In another known method synthesizing metal oxide inks and films for electronic devices, the metal oxide, for instance, MoO3, was prepared by oxidizing the metal-ligand inks by heating or light irradiation or active oxygen exposure. The metal-ligand inks were prepared using metal complexes and organic solvents, which consist of carbonyl groups and/or hydroxyl groups. Unfortunately, both preparation methods are time consuming. Toxic organic compounds and solvents were also needed for these processes. In a separate investigation, a solution-processed MoO3 layer for OPV cells was prepared by spin-coating an aqueous MoO3 solution. The solution was prepared from (NH4)6Mo7O24 (ammonium molybdate) and hydrochloric acid solution. However, the ink is highly acidic, which can etch the indium tin oxide (ITO) electrodes.
- Therefore, there remains a need to provide for alternative solution-based methods of forming molybdenum oxide films for optoelectronic applications.
- In a first aspect, there is disclosed an ink for forming a hybrid molybdenum (VI) oxide (MoO3) film on a substrate, the ink comprising:
- an ammonium molybdate;
at least one inorganic salt different from ammonium molybdate; and
a solvent or a solvent mixture. - In various embodiments, the ammonium molybdate is (NH4)6Mo7O24.
- In various embodiments, the inorganic salt is a metal halide, such as zinc chloride or calcium chloride.
- In a second aspect, there is disclosed a method for preparing a molybdenum (VI) oxide (MoO3) coating ink, the method comprising:
- mixing a molybdate compound and an inorganic salt in a solution;
mixing a solution of molybdate compound and an inorganic salt;
mixing a molybdate compound and a solution of an inorganic salt; or
mixing a solution of a molybdate compound and a solution of an inorganic salt. - In a third aspect, there is disclosed a method for forming a hybrid molybdenum (VI) oxide (MoO3) film on a substrate, the method comprising:
- coating the substrate with an ink to form a film; and
annealing the film,
wherein the ink comprises an ammonium molybdate, at least one inorganic salt different from ammonium molybdate, and a solvent or a solvent mixture. - In a fourth aspect, there is disclosed an optoelectronic device comprising a hybrid molybdenum (VI) oxide (MoO3) film coated substrate formed by coating a substrate with an ink to form a film and annealing the film, wherein the ink comprises an ammonium molybdate, at least one inorganic salt different from ammonium molybdate, and a solvent or a solvent mixture.
- In the drawings, like reference characters generally refer to the same parts throughout the different views. The drawings are not necessarily drawn to scale, emphasis instead generally being placed upon illustrating the principles of various embodiments. In the following description, various embodiments of the invention are described with reference to the following drawings.
-
FIG. 1 shows the morphology of (a) pure ITO; (b) MoO3 film coated onto ITO from ammonium molydate ink; and (c) hybridized MoO3 film coated onto ITO from ammonium molydate ink with ZnCl2. Scan area is 1×1 μm. -
FIG. 2 shows the cross-section of the OPV device under investigation. The OPV device can be formed of a normal (or forward) structure configuration shown inFIG. 2A where different types of hybridized MoO3 films functioning as the hole-transporting layer were coated onto ITO glass. The OPV device can also be formed of an inverted structure configuration shown inFIG. 2B . -
FIG. 3 shows the comparison of cell performances with pure MoO3 film as the hole-transporting layer (marked as A) and a PEDOT:PSS control device. -
FIG. 4 shows the comparison of cell performances with MoO3 films as the hole-transporting layer: MoO3 film (B) prepared from ammonium molybdate ink with ZnCl2 additive; MoO3 film (C) prepared from ammonium molybdate ink with CaCl2 additive. -
FIG. 5 shows the comparison of cell performances with MoO3 films as the hole-transporting layer: MoO3 film (D) prepared from ammonium molybdate ink with HCl; MoO3 film (E) prepared from ammonium molybdate ink with HCl and ZnCl2 additive. -
FIG. 6 shows a scheme showing the method for the preparation of hybridized molybdenum oxide (H—Mo) films. -
FIG. 7 shows preliminary lifetime studies, demonstrating that H—MoO3 OPV devices are generally more stable. - The following detailed description refers to the accompanying drawings that show, by way of illustration, specific details and embodiments in which the invention may be practised. These embodiments are described in sufficient detail to enable those skilled in the art to practise the invention. Other embodiments may be utilized and structural, logical, and electrical changes may be made without departing from the scope of the invention. The various embodiments are not necessarily mutually exclusive, as some embodiments can be combined with one or more other embodiments to form new embodiments.
- Present inventors have developed solution-based methods of forming molybdenum (VI) oxide (MoO3) films for optoelectronic applications, such as but not limited to, organic photovoltaic (OPV) devices. In present methods, a combination of additives to prepare MoO3 films from inks is used, and such preparation methods have helped to improve the performance of OPV devices.
- MoO3 films are prepared from ammonium molybdate inks with soluble inorganic salts as additives, producing comparable cell performances at a less acidic ink condition. The solution-processable MoO3 film is environment friendly since water is employed as the formulation solvent. The formation of the MoO3 film is processed at relatively low temperatures for a short period of time. By applying the MoO3 film as a hole-transporting layer in OPV devices, the overall solar cell efficiency can be improved.
- Thus, in a first aspect, the present invention relates to an ink for forming a hybrid MoO3 film on a substrate. The ink comprises an ammonium molybdate, at least one inorganic salt different from ammonium molybdate, and a solvent or a solvent mixture.
- In various embodiments, the ammonium molybdate may be selected from the group consisting of ammonium heptamolybdate ((NH4)6Mo7O24), ammonium dimolybdate ((NH4)2Mo2O7), ammonium orthomolybdate ((NH4)2MoO4), (NH4)4Mo5O17, (NH4)2Mo4O13, β-(NH4)2Mo4O13, (NH4)4Mo8O26, (NH4)4Mo8O26, (NH4)2Mo14O43, (NH4)2Mo22O67 and hydrates thereof.
- In one embodiment, the ammonium molybdate is (NH4)6Mo7O24.
- In various embodiments, the inorganic salts comprise soluble inorganic salts containing transition metal ions and counter ions. In various embodiments, the inorganic salt is a metal halide. The metal can be selected from zinc, calcium, beryllium, magnesium, strontium, barium, radium, cadmium, mercury, and copernicium. The halogen ion can be selected from fluoride, chloride, bromide and iodide. In particular, the metal halide can be selected from the group consisting of zinc chloride, zinc bromide, zinc iodide, calcium chloride, calcium bromide, calcium iodide, beryllium chloride, beryllium bromide, beryllium iodide, magnesium chloride, magnesium bromide, magnesium iodide, strontium chloride, strontium bromide, strontium iodide, barium chloride, barium bromide, barium iodide, radium chloride, radium bromide, radium iodide, cadmium chloride, cadmium bromide, cadmium iodide, mercury chloride, mercury bromide, mercury iodide, copernicium chloride, copernicium bromide, and copernicium iodide.
- In one embodiment, the inorganic salt may be zinc chloride or calcium chloride.
- In various embodiments, the solvent is a polar solvent selected from the group consisting of water, alcohols, furan, esters, acetonitrile, acetone, dimethylformamide, dimethyl sulfoxide and mixture thereof.
- In one embodiment, the solvent is water.
- In alternative embodiments, the solvent is furan or an alcohol.
- In various embodiments, the ink further comprises an acid. The acid may be selected from the group consisting of hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, nitric acid, chloric acid, chlorous acid, sulfurous acid, hydrocyanic acid, perchloric acid, phosphoric acid, hypophosphorous acid, and boric acid.
- In one specific embodiment, the acid is hydrogen chloride.
- In various embodiments, the pH of the ink is at least 1. For example, the pH of the ink may be 1, 1.5, 2, 2.5, 3, 3.3, 4, 4.5, 5, 5.3, or 6 and even higher.
- In a second aspect, the present invention relates to a method of preparing a MoO3 coating ink of the first aspect, the method comprising (i) mixing a molybdate compound and an inorganic salt in a solution, or (ii) mixing a solution of molybdate compound and an inorganic salt, or (iii) mixing a molybdate compound and a solution of an inorganic salt, or (iv) mixing a solution of a molybdate compound and a solution of an inorganic salt.
- In various embodiments, the method of preparing the molybdenum oxide coating ink further comprises adding an acid to the mixture. The acid may be selected from the group consisting of hydrogen chloride, hydrogen bromide, hydrogen iodide, sulfuric acid, nitric acid, chloric acid, chlorous acid, sulfurous acid, hydrocyanic acid, perchloric acid, phosphoric acid, hypophosphorous acid, and boric acid.
- In a third aspect, the present invention relates to a method of forming a hybrid MoO3 film on a substrate, the method comprising coating the substrate with an ink according to the first aspect to form a film, and annealing the film.
- In various embodiments, coating the substrate is solution-based. For example, the solution-based coating and/or printing technique may be selected from the group consisting of spin coating, slot die coating, inkjet printing, dispensing, spray coating, blade coating, doctor blading, knife coating, curtain coating, gravure printing, flexo printing, offset printing, screen printing, and pad printing.
- In one embodiment,
FIG. 6 shows a scheme showing the method for the preparation of hybridized MoO3 (H—Mo) films. Briefly, a molybdenum compound or salt (e.g. (NH4)6Mo7O24 which is a cheap and commercially available salt) is first dissolved in a solvent (e.g. water which is green and sustainable) to form a Mo ink. Next, common salts additives such as ZnCl2 or CaCl2 (which are cheap and easily available) are added to the Mo ink to form a H—Mo (hybrid) ink. The H—Mo ink is then processed, for example using printing and coating techniques described above, to make OPV devices. The thus-fabricated OPV devices may be rigid or flexible. The entire process is conducted at low process temperature with a high throughput and the advantages in employing such process include a green, low-cost technique, and solution-based printable technique, yielding improved OPV device efficiency and life time. Additionally, the H—Mo ink can be processed before or after forming the active layer depending on the normal or inverted OPV configuration, which gives great flexibility and advantage for OPV fabrication and performance optimization. - In one embodiment, the ink may be slot die coated onto the substrate.
- In various embodiments, the substrate may be flexible or rigid.
- In various embodiments, the substrate may be glass, paper/synthetic paper and plastic films such as PEN, PET, or polyimide.
- In one embodiment, the substrate may be indium tin oxide (ITO) patterned glass substrate.
- In various embodiments, the film may be annealed at a temperature between 50 and 500° C.
- In various embodiments, the thickness of the film may be at least 1 nm. For example, the thickness of the film may be 1 nm, 10 nm, 25 nm, 50 nm, 75 nm, 100 nm, 125 nm, 150 nm, 175 nm, 200 nm, 300 nm, 400 nm, 500 nm, 600 nm, 700 nm, 800 nm, 900 nm, 1 μm and even higher.
- In a fourth aspect, the present invention relates to the hybrid MoO3 film coated substrate prepared according to the third aspect.
- In a fifth aspect, the present invention relates to an optoelectronic device comprising the hybrid MoO3 film coated substrate according to the fourth aspect. The optoelectronic device can be formed of a normal configuration or an inverted configuration.
- In a normal configuration optoelectronic device, the conductive substrate (i.e. substrate with a conductive coating) forms the anode and the hybrid MoO3 film forms the hole-transporting layer (conductive layer; charge transport layer). The optoelectronic device may further comprise an active layer formed on the MoO3 film and a cathode layer. As illustrated in
FIG. 2A , the structure sequence of the normal configuration optoelectronic device is anode/hole-transporting layer/active layer/cathode. - In one embodiment of such a device, the conductive substrate forming the anode may comprise or consist of ITO.
- In one embodiment, the active layer may be poly (3-hexylthiophene) and [6,6]-phenyl C61-butyric acid methyl ester (P3HT:PCBM).
- In one embodiment, the cathode layer may be aluminium metal.
- In an inverted configuration optoelectronic device, the device comprises a cathode, an electron transporting layer formed on the cathode, an active layer formed on the electron transporting layer, the hybrid MoO3 film forming a hole transporting layer formed on the active layer, and an anode formed on the hybrid MoO3 film. In the specific embodiment illustrated in
FIG. 2B , the structure sequence of the inverted configuration optoelectronic device is ITO glass/ZnO/P3HT:PCBM/H—MoO3/Ag wherein the cathode is ITO glass, the electron transport layer is ZnO, the active layer is P3HT:PCBM and the anode is Ag. - In various embodiments, the optoelectronic device may be a printed electronic device, sensor, or chromic window.
- In certain embodiments, the optoelectronic device may be a printed electronic device. For example, the printed electronic device may be a photoelectrical device, photoelectrical sensor, photovoltaic, organic photovoltaic, thin film transistor, organic thin film transistor, light emitting device, light emitting diode, organic light emitting diode, thermochromic, photochromic, electrochromic, or optoelectric sensor related optoelectronic devices.
- In various embodiments, the inorganic material of the photoelectrical device, photoelectrical sensor, photovoltaic, thin film transistor, light emitting device, light emitting diode, thermochromic, photochromic, electrochromic, optoelectric sensor related optoelectronic devices may be inorganic functional materials.
- In various embodiments, the organic material of the photoelectrical device, photoelectrical sensor, photovoltaic, thin film transistor, light emitting device, light emitting diode, thermochromic, photochromic, electrochromic, optoelectric sensor related optoelectronic devices may be small molecules or polymeric materials.
- In various embodiments, the hybrid material of the photoelectrical device, photoelectrical sensor, photovoltaic, thin film transistor, light emitting device, light emitting diode, thermochromic, photochromic, electrochromic, optoelectric sensor related optoelectronic devices includes a combination of inorganic and organic functional materials.
- In various embodiments, the optoelectronic device may be of normal configuration or inverted configuration.
- In one illustrated embodiment, a PCE comparable to our control cells, using PEDOT:PSS as the hole-transporting layer, has been achieved. Utilizing a combination of HCl and ZnCl2 as additives yields a PCE of 3.09%. This value is comparable to our control OPV device, which has a PCE of 3.14% (see Table 3 below).
- In order that the invention may be readily understood and put into practical effect, particular embodiments will now be described by way of the following non-limiting examples.
- The procedure to prepare hybridized MoO3 films is described in
FIG. 6 . 230.8 mg of (NH4)6Mo7O24 was dissolved in 10 ml of water to attain a concentration of 0.3 M. This ink was marked as A and its pH value is 5.3. Next, 60 μl of aqueous zinc chloride (ZnCl2) was added to ink A. This ink was marked as B and its pH value is 5.3. Both inks were spin-coated onto indium tin oxide (ITO) substrates. - The films were analyzed by atomic force microscopy (AFM), which revealed that the molybdenum oxide films were deposited onto the ITO substrate surface. A significant change in the morphology is observed. AFM images seem to suggest that there is a roughening of the ITO surface after the films are fabricated (
FIG. 1 ). The thickness of the films is 10 nm, which was determined by ellipsometry. - In this example, an OPV device having a normal configuration is first described. Both P3HT and PCBM were dissolved in 1,2-dichlorobenzene (DCB) solution in a ratio of 1:0.8. Devices were prepared on ITO patterned glass substrate. The ITO patterned glass substrates were first sonicated in a detergent bath for half an hour, followed by a rinsing of de-ionized water for 20 min. This was succeeded by sonicating in an acetone and isoproponal bath for 15 min and 20 min, respectively. The cleaning step was concluded by drying the substrates in an oven at 80° C. for at least an hour. The substrates were subjected to an ozone plasma treatment for 10 min before the MoO3 inks were spin-coated. Annealing was done at 150° C. for 10 min. Ellipsometric data reveals that the thickness of the MoO3 layers was approximately 10 nm. Annealing was performed at 120° C. for 10 min. Next, the active layer of P3HT:PCBM was spin-coated and allowed to dry for 2 hours before being annealed at 120° C. for 10 min, yielding a film thickness of ˜200 nm. Lastly, a 100 nm thick Al as the cathode were deposited via an MBraun evaporation system at a pressure less than 10−3 Pa. The active area of the device was 9 mm2. The device structure is shown in
FIG. 2A . For the control device, a 45 nm thick PEDOT:PSS was spin-coated onto the ITO surface. Pure MoO3 ink is prepared directly from (NH4)6Mo7O24. - In an alternative embodiment, an inverted configuration OPV device is shown in
FIG. 2B . In this embodiment, the structure sequence consists of ITO glass/ZnO/P3HT:PCBM/H—MoO3/Ag (i.e. cathode/electron transporting layer/active layer/hole transporting layer/anode). The H—Mo ink can be processed before or after forming the active layer depending on the normal or inverted OPV configuration, which gives great flexibility and advantage for OPV fabrication and performance optimization. - For the purposes of illustration, the examples and experimental results described herein relate to normal configuration OPV devices, unless stated otherwise.
- The I-V curves are shown in
FIG. 3 and the cell performance results are summarized in Table 1. Upon replacing PEDOT:PSS with MoO3 film prepared from ammonium molybdate ink, the power conversion efficiency (PCE) drops from 3.14% to 1.12% (Table 1, A). -
TABLE 1 Cell Performances of OPV Devices with Pure MoO3 Film as the Hole-Transporting Layer (A) and PEDOT:PSS Voc (V) Jsc (mA/cm2) FF PCE (%) PEDOT:PSS 0.55 9.10 0.63 3.14 (Control) A 0.48 4.38 0.53 1.12 - The trend can be reversed in Example 2 if the MoO3 film is hybridized. They are prepared as ink B and ink C, which has a pH value of 5.3 and 5.2, respectively Ink B was prepared from ammonium molybdate ink with ZnCl2 as the additive. The I-V curves are plotted in
FIG. 4 and the figures merits are summarized in Table 2. An improvement is observed, with its PCE rising to 2.12% (Table 2, B). The cell efficiency was improved by 89%. An 80% improvement in the cell performance can be observed by hybridizing MoO3 with CaCl2 additive (Table 2, C). In this case, a PCE of 2.02% is obtained. -
TABLE 2 Cell Performances of OPV Devices with MoO3 Films as the Hole- Transporting Layer. Ink B is marked as MoO3 film prepared from ammonium molybdate ink with ZnCl2 additive; Ink C is marked as MoO3 film prepared from ammonium molybdate ink with CaCl2 additive. Voc (V) Jsc (mA/cm2) FF PCE (%) PEDOT:PSS 0.55 9.10 0.63 3.14 (Control) A 0.48 4.38 0.53 1.12 B 0.53 6.81 0.58 2.12 C 0.53 6.36 0.60 2.02 - In this example, MoO3 films were prepared as ink D and ink E, having a pH value of 3.6 and 3.5, respectively.
- In a bid to further improve the performance of MoO3-based OPV cells, HCl as an additive was introduced. It has been found that efficiency of OPV cells can be improved by using HCl as an additive. Two different samples were prepared for comparisons: HCl and HCl+ZnCl2 as the additives in the ammonium molybdate inks. The thickness of the P3HT:PCBM layer was kept the same as the data in Table 2. As shown in Table 3 below, a further improvement is observed. The I-V curves are plotted in
FIG. 5 . In fact, by using MoO3 films prepared from ammonium molybdate ink with a combination of HCl and ZnCl2 additives, OPV performance was elevated a notch further as compared to a system when only HCl as additive to ammonium molybdate ink was used. An increase in the PCE from 2.86% to 3.09% has shown that it is possible to further enhance the performance of OPV devices by utilizing a blend of HCl and a salt compound. In fact, results are comparable to the control cell, which uses PEDOT:PSS in Table 1. -
TABLE 3 Cell Performances of OPV Devices with MoO3 Films as the Hole- Transporting Layer. Ink D is marked as MoO3 film prepared from ammonium molybdate ink with HCl; Ink E is marked as MoO3 film prepared from ammonium molybdate ink with HCl and ZnCl2 additive. Voc (V) Jsc (mA/cm2) FF PCE (%) PEDOT:PSS 0.55 9.10 0.63 3.14 (Control) A 0.48 4.38 0.53 1.12 D 0.54 8.54 0.62 2.86 E 0.55 8.88 0.63 3.09 - Based on the promising results above, present inventors have demonstrated that there is an alternative to PEDOT:PSS as the hole-transporting layer. In fact, further optimization by exploring the usage of other salt compounds could even further raise the performance of OPV devices. Such a method could mean a potential replacement of PEDOT:PSS in the future.
- It has to be emphasized about the role of ZnCl2 in the HCl and ZnCl2 combination for the cell performance. ZnCl2 helps to improve the cell efficiency by 8%. At the same time, PEDOT:PSS has a pH value of ˜1.6 while MoO3 hybridized with HCl and ZnCl2 has helped to lift the pH value to 3.5 The usage of other salts such as CaCl2 can be expected to produce the same observation as well.
- By “comprising” it is meant including, but not limited to, whatever follows the word “comprising”. Thus, use of the term “comprising” indicates that the listed elements are required or mandatory, but that other elements are optional and may or may not be present.
- By “consisting of” is meant including, and limited to, whatever follows the phrase “consisting of”. Thus, the phrase “consisting of” indicates that the listed elements are required or mandatory, and that no other elements may be present.
- The inventions illustratively described herein may suitably be practiced in the absence of any element or elements, limitation or limitations, not specifically disclosed herein. Thus, for example, the terms “comprising”, “including”, “containing”, etc. shall be read expansively and without limitation. Additionally, the terms and expressions employed herein have been used as terms of description and not of limitation, and there is no intention in the use of such terms and expressions of excluding any equivalents of the features shown and described or portions thereof, but it is recognized that various modifications are possible within the scope of the invention claimed. Thus, it should be understood that although the present invention has been specifically disclosed by preferred embodiments and optional features, modification and variation of the inventions embodied therein herein disclosed may be resorted to by those skilled in the art, and that such modifications and variations are considered to be within the scope of this invention.
- By “about” in relation to a given numerical value, such as for temperature and period of time, it is meant to include numerical values within 10% of the specified value.
- The invention has been described broadly and generically herein. Each of the narrower species and sub-generic groupings falling within the generic disclosure also form part of the invention. This includes the generic description of the invention with a proviso or negative limitation removing any subject matter from the genus, regardless of whether or not the excised material is specifically recited herein.
- Other embodiments are within the following claims and non-limiting examples. In addition, where features or aspects of the invention are described in terms of Markush groups, those skilled in the art will recognize that the invention is also thereby described in terms of any individual member or subgroup of members of the Markush group.
Claims (10)
1. A method for forming a hybrid molybdenum (VI) oxide (MoO3) film on a substrate, the method comprising:
coating the substrate with an ink to form a film; and
annealing the film,
wherein the ink comprises an ammonium molybdate, at least one inorganic salt different from ammonium molybdate, and a solvent or a solvent mixture.
2. The method of claim 1 , wherein the coating step is solution-based.
3. The method of claim 2 , wherein the solution-based coating step is selected from the group consisting of spin coating, slot die coating, inkjet printing, dispensing, spray coating, blade coating, doctor blading, knife coating, curtain coating, gravure printing, flexo printing, offset printing, screen printing, and pad printing.
4. The method of claim 3 , wherein the ink is slot die coated onto the substrate.
5. The method of claim 1 , wherein the substrate is flexible or rigid.
6. The method of claim 5 , wherein the substrate is glass, paper/synthetic paper or plastic film.
7. The method of claim 6 , wherein the substrate is a plastic film selected from the group consisting of PEN, PET, and polyimide.
8. The method of claim 6 , wherein the substrate is indium tin oxide patterned glass substrate.
9. The method of claim 1 , wherein the film is annealed at a temperature of between 50 and 500° C.
10. The method of claim 1 , wherein the thickness of the film is at least 1 nm.
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US9373804B2 (en) | 2016-06-21 |
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