JPWO2020084285A5 - - Google Patents
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- JPWO2020084285A5 JPWO2020084285A5 JP2021521523A JP2021521523A JPWO2020084285A5 JP WO2020084285 A5 JPWO2020084285 A5 JP WO2020084285A5 JP 2021521523 A JP2021521523 A JP 2021521523A JP 2021521523 A JP2021521523 A JP 2021521523A JP WO2020084285 A5 JPWO2020084285 A5 JP WO2020084285A5
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- crystalline
- photoactive
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- layer
- charge recombination
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- 239000000463 material Substances 0.000 claims description 93
- 238000005215 recombination Methods 0.000 claims description 50
- 239000000758 substrate Substances 0.000 claims description 41
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 38
- 150000001768 cations Chemical class 0.000 claims description 38
- 150000001412 amines Chemical class 0.000 claims description 26
- 239000002105 nanoparticle Substances 0.000 claims description 22
- -1 metalloid cations Chemical class 0.000 claims description 20
- 125000000217 alkyl group Chemical group 0.000 claims description 18
- IAZDPXIOMUYVGZ-UHFFFAOYSA-N dimethylsulphoxide Chemical compound CS(C)=O IAZDPXIOMUYVGZ-UHFFFAOYSA-N 0.000 claims description 18
- 229920001940 conductive polymer Polymers 0.000 claims description 16
- 239000002904 solvent Substances 0.000 claims description 16
- 150000001875 compounds Chemical class 0.000 claims description 14
- 239000000203 mixture Substances 0.000 claims description 14
- 239000000010 aprotic solvent Substances 0.000 claims description 12
- 239000011159 matrix material Substances 0.000 claims description 12
- 229910052751 metal Inorganic materials 0.000 claims description 12
- 239000002184 metal Substances 0.000 claims description 12
- 150000001450 anions Chemical class 0.000 claims description 10
- WEVYAHXRMPXWCK-UHFFFAOYSA-N acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 8
- 125000003118 aryl group Chemical group 0.000 claims description 8
- 239000006185 dispersion Substances 0.000 claims description 8
- AMGQUBHHOARCQH-UHFFFAOYSA-N indium;oxotin Chemical compound [In].[Sn]=O AMGQUBHHOARCQH-UHFFFAOYSA-N 0.000 claims description 8
- 229910052752 metalloid Inorganic materials 0.000 claims description 8
- 230000005693 optoelectronics Effects 0.000 claims description 7
- ZWEHNKRNPOVVGH-UHFFFAOYSA-N 2-butanone Chemical compound CCC(C)=O ZWEHNKRNPOVVGH-UHFFFAOYSA-N 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 claims description 4
- MVPPADPHJFYWMZ-UHFFFAOYSA-N Chlorobenzene Chemical compound ClC1=CC=CC=C1 MVPPADPHJFYWMZ-UHFFFAOYSA-N 0.000 claims description 4
- 229920001609 Poly(3,4-ethylenedioxythiophene) Polymers 0.000 claims description 4
- CSCPPACGZOOCGX-UHFFFAOYSA-N acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 4
- 150000002431 hydrogen Chemical class 0.000 claims description 4
- 125000000250 methylamino group Chemical group [H]N(*)C([H])([H])[H] 0.000 claims description 4
- BAVYZALUXZFZLV-UHFFFAOYSA-O methylammonium Chemical compound [NH3+]C BAVYZALUXZFZLV-UHFFFAOYSA-O 0.000 claims description 4
- 229920001467 poly(styrenesulfonates) Polymers 0.000 claims description 4
- 229960002796 polystyrene sulfonate Drugs 0.000 claims description 4
- 239000011970 polystyrene sulfonate Substances 0.000 claims description 4
- YXFVVABEGXRONW-UHFFFAOYSA-N toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 4
- 239000002585 base Substances 0.000 claims description 3
- 239000002322 conducting polymer Substances 0.000 claims description 3
- 125000004890 (C1-C6) alkylamino group Chemical group 0.000 claims description 2
- 125000006376 (C3-C10) cycloalkyl group Chemical group 0.000 claims description 2
- 125000005913 (C3-C6) cycloalkyl group Chemical group 0.000 claims description 2
- BHHGXPLMPWCGHP-UHFFFAOYSA-N 2-Phenethylamine Chemical compound NCCC1=CC=CC=C1 BHHGXPLMPWCGHP-UHFFFAOYSA-N 0.000 claims description 2
- WGQKYBSKWIADBV-UHFFFAOYSA-N Benzylamine Chemical compound NCC1=CC=CC=C1 WGQKYBSKWIADBV-UHFFFAOYSA-N 0.000 claims description 2
- 125000000882 C2-C6 alkenyl group Chemical group 0.000 claims description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-N Hexylamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-N N-Butylamine Chemical compound CCCCN HQABUPZFAYXKJW-UHFFFAOYSA-N 0.000 claims description 2
- 229920000144 PEDOT:PSS Polymers 0.000 claims description 2
- 229940100684 PENTYLAMINE Drugs 0.000 claims description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-N Pentylamine Chemical compound CCCCCN DPBLXKKOBLCELK-UHFFFAOYSA-N 0.000 claims description 2
- FIGVSQKKPIKBST-UHFFFAOYSA-N Phenyl-C61-butyric acid methyl ester Chemical compound C12=C3C4=C5C2=C2C6=C7C1=C1C8=C3C=3C9=C4C4=C%10C5=C5C2=C2C6=C6C%11=C7C1=C1C7=C8C=3C3=C8C9=C4C4=C9C%10=C5C5=C2C2=C6C6=C%11C1=C1C7=C3C=3C8=C4C4=7C9=C5C2=C2C6=C1C=3C2=7C4(CCCC(=O)OC)C1=CC=CC=C1 FIGVSQKKPIKBST-UHFFFAOYSA-N 0.000 claims description 2
- FVSKHRXBFJPNKK-UHFFFAOYSA-N Propionitrile Chemical compound CCC#N FVSKHRXBFJPNKK-UHFFFAOYSA-N 0.000 claims description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-N Propylamine Chemical compound CCCN WGYKZJWCGVVSQN-UHFFFAOYSA-N 0.000 claims description 2
- 229910052783 alkali metal Inorganic materials 0.000 claims description 2
- 150000003973 alkyl amines Chemical class 0.000 claims description 2
- 125000005210 alkyl ammonium group Chemical group 0.000 claims description 2
- 125000005277 alkyl imino group Chemical group 0.000 claims description 2
- 150000004982 aromatic amines Chemical class 0.000 claims description 2
- HQABUPZFAYXKJW-UHFFFAOYSA-O butylazanium Chemical compound CCCC[NH3+] HQABUPZFAYXKJW-UHFFFAOYSA-O 0.000 claims description 2
- ROSDSFDQCJNGOL-UHFFFAOYSA-O dimethylaminium Chemical compound C[NH2+]C ROSDSFDQCJNGOL-UHFFFAOYSA-O 0.000 claims description 2
- OQLZINXFSUDMHM-UHFFFAOYSA-O ethanimidoylazanium Chemical compound CC(N)=[NH2+] OQLZINXFSUDMHM-UHFFFAOYSA-O 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-N ethyl amine Chemical compound CCN QUSNBJAOOMFDIB-UHFFFAOYSA-N 0.000 claims description 2
- QUSNBJAOOMFDIB-UHFFFAOYSA-O ethylaminium Chemical compound CC[NH3+] QUSNBJAOOMFDIB-UHFFFAOYSA-O 0.000 claims description 2
- ZRALSGWEFCBTJO-UHFFFAOYSA-O guanidinium Chemical compound NC(N)=[NH2+] ZRALSGWEFCBTJO-UHFFFAOYSA-O 0.000 claims description 2
- 150000004820 halides Chemical class 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- WJYIASZWHGOTOU-UHFFFAOYSA-O heptylazanium Chemical compound CCCCCCC[NH3+] WJYIASZWHGOTOU-UHFFFAOYSA-O 0.000 claims description 2
- BMVXCPBXGZKUPN-UHFFFAOYSA-O hexylazanium Chemical compound CCCCCC[NH3+] BMVXCPBXGZKUPN-UHFFFAOYSA-O 0.000 claims description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 2
- 125000001841 imino group Chemical group [H]N=* 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- PNKUSGQVOMIXLU-UHFFFAOYSA-N methanoic acid amidine Chemical compound NC=N PNKUSGQVOMIXLU-UHFFFAOYSA-N 0.000 claims description 2
- BAVYZALUXZFZLV-UHFFFAOYSA-N methylamine Chemical compound NC BAVYZALUXZFZLV-UHFFFAOYSA-N 0.000 claims description 2
- IOQPZZOEVPZRBK-UHFFFAOYSA-N octan-1-amine Chemical compound CCCCCCCCN IOQPZZOEVPZRBK-UHFFFAOYSA-N 0.000 claims description 2
- 150000002892 organic cations Chemical class 0.000 claims description 2
- DPBLXKKOBLCELK-UHFFFAOYSA-O pentylazanium Chemical compound CCCCC[NH3+] DPBLXKKOBLCELK-UHFFFAOYSA-O 0.000 claims description 2
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 claims description 2
- 239000003880 polar aprotic solvent Substances 0.000 claims description 2
- 229920000642 polymer Polymers 0.000 claims description 2
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 claims description 2
- WGYKZJWCGVVSQN-UHFFFAOYSA-O propan-1-aminium Chemical compound CCC[NH3+] WGYKZJWCGVVSQN-UHFFFAOYSA-O 0.000 claims description 2
- 238000004528 spin coating Methods 0.000 claims description 2
- 125000001424 substituent group Chemical group 0.000 claims description 2
- QEMXHQIAXOOASZ-UHFFFAOYSA-N tetramethylammonium Chemical compound C[N+](C)(C)C QEMXHQIAXOOASZ-UHFFFAOYSA-N 0.000 claims description 2
- GETQZCLCWQTVFV-UHFFFAOYSA-O trimethylammonium Chemical compound C[NH+](C)C GETQZCLCWQTVFV-UHFFFAOYSA-O 0.000 claims description 2
- UUIQMZJEGPQKFD-UHFFFAOYSA-N Methyl butyrate Chemical compound CCCC(=O)OC UUIQMZJEGPQKFD-UHFFFAOYSA-N 0.000 claims 1
- 238000000151 deposition Methods 0.000 claims 1
- ZHNUHDYFZUAESO-UHFFFAOYSA-N formamide Chemical compound NC=O ZHNUHDYFZUAESO-UHFFFAOYSA-N 0.000 description 2
- 239000003990 capacitor Substances 0.000 description 1
- 125000000118 dimethyl group Chemical group [H]C([H])([H])* 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
Description
典型的には、本明細書に記載の多接合デバイスは、光電子(オプトエレクトロニクス)デバイス、光起電力デバイス、太陽電池、光検出器、フォトダイオード、光センサー、発色デバイス、トランジスタ、感光トランジスタ、フォトトランジスタ、固体三極管、電池、電池電極、コンデンサ、超コンデンサ、発光デバイス、発光ダイオード及びレーザーからなる群から選択される。例えば、多接合デバイスは光電子デバイスであってもよい。光電子デバイスの例としては、光起電力デバイス、フォトダイオード(太陽電池を含む)、フォトトランジスタ、光電子増倍器、フォトレジスター及び発光デバイスが挙げられる。好ましくは、多接合デバイスは、光起電力デバイス又は発光デバイスである。
いくつかの実施形態を以下に示す。
項１
結晶A/M/X材料の層を含む多接合デバイスを製造する方法であって、結晶A/M/X材料が式[A]
a
[M]
b
[X]
c
(式中、
[A]は、1つ以上のAカチオンを含み、
[M]は、金属又は半金属のカチオンである1つ以上のMカチオンを含み、
[X]は、1つ以上のXアニオンを含み、
aは1～6の数であり、
bは1～6の数であり、
cは1～18の数である)
の化合物を含み、前記方法が、膜形成溶液を基材上に配置することにより前記結晶A/M/X材料の層を形成する工程を含み、ここで、前記膜形成溶液は、
(a)1つ以上のMカチオン、及び
(b)溶媒
を含み、前記溶媒は、
(i)非プロトン性溶媒、及び
(ii)有機アミン
を含み、前記基材は、
光活性材料を含む光活性領域、及び
溶液堆積法により前記光活性領域上に配置される電荷再結合層
を含む、方法。
項２
前記非プロトン性溶媒が、極性非プロトン性溶媒である、項1に記載の方法。
項３
前記基材が、前記電荷再結合層上に配置される電荷輸送材料の層をさらに含む、項1又は2に記載の方法。
項４
前記電荷再結合層を溶液堆積法により前記光活性領域上に配置する工程、及び
任意選択で、電荷輸送材料の層を前記電荷再結合層上に配置する工程
により、前記基材を製造する工程を含む、項1から3のいずれか一項に記載の方法。
項５
前記基材中の前記光活性材料が、ジメチルホルムアミド(DMF)、ジメチルスルホキシド(DMSO)若しくはこれらの混合物中に溶解する、又は前記基材中の前記電荷再結合層の少なくとも1つの成分が、ジメチルホルムアミド(DMF)、ジメチルスルホキシド(DMSO)若しくはこれらの混合物中に溶解し、
好ましくは、前記基材中の前記光活性材料と前記基材中の前記電荷再結合層の少なくとも1つの成分との両方が、ジメチルホルムアミド(DMF)、ジメチルスルホキシド(DMSO)又はこれらの混合物中に溶解し、
より好ましくは、前記基材中の前記光活性材料と前記基材中の前記電荷再結合層との両方が、ジメチルホルムアミド(DMF)、ジメチルスルホキシド(DMSO)又はこれらの混合物中に溶解する、項1～4のいずれか一項に記載の方法。
項６
前記電荷再結合層が透明導電性酸化物のナノ粒子を含み、任意選択で、前記透明導電性酸化物がインジウムスズ酸化物(ITO)を含む、項1～5のいずれか一項に記載の方法。
項７
前記透明導電性酸化物のナノ粒子がマトリックス材料、例えば有機マトリックス材料、任意選択で、電子輸送有機マトリックス材料中に配置され、任意選択で、前記有機マトリックス材料が[6,6]-フェニル-C61-酪酸メチルエステル(PCBM)を含む、項6に記載の方法。
項８
前記電荷再結合層が導電性ポリマーをさらに含み、好ましくは、前記導電性ポリマーが、ポリ(3,4-エチレンジオキシチオフェン)及びポリスチレンスルホネート(PEDOT:PSS)を含む、項6又は7に記載の方法。
項９
前記電荷再結合層を前記光活性領域上に配置する工程が、透明導電性酸化物のナノ粒子の溶媒分散体を前記光活性領域上に配置する工程を含み、好ましくは、前記電荷再結合層を前記光活性領域上に配置する工程が、導電性ポリマーを前記光活性領域上に配置する工程、及び透明導電性酸化物のナノ粒子の溶媒分散体を前記光活性領域上に配置する工程を含み、任意選択で、前記ナノ粒子の溶媒分散体が、マトリックス材料、例えば有機マトリックス材料をさらに含み、任意選択で、前記ナノ粒子の溶媒分散体及び/又は前記導電性ポリマーが、スピンコーティングにより前記光活性領域上に配置される、項4～8のいずれか一項に記載の方法。
項１０
前記非プロトン性溶媒がジメチルホルムアミドを含まず、好ましくは、前記非プロトン性溶媒が、ジメチルホルムアミド、ジメチルスルホキシド又はこれらの混合物を含まない、項1～9のいずれか一項に記載の方法。
項１１
前記非プロトン性溶媒が、クロロベンゼン、アセトン、ブタノン、メチルエチルケトン、アセトニトリル、プロピオニトリル、トルエン又はこれらの混合物からなる群から選択される化合物を含み、好ましくは、前記非プロトン性溶媒がアセトニトリルを含む、項1～10のいずれか一項に記載の方法。
項１２
前記有機アミンが、非置換若しくは置換アルキルアミン又は非置換若しくは置換アリールアミンである、項1～11のいずれか一項に記載の方法。
項１３
前記有機アミンが非置換又は置換(C
1～10
アルキル)アミンであり、好ましくは前記有機アミンが、非置換(C
1～10
アルキル)アミン又はフェニル基で置換されている(C
1～10
アルキル)アミンであり、より好ましくは前記有機アミンが、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン若しくはペンチルアミン若しくはヘキシルアミン、ベンジルアミン又はフェニルエチルアミンであり、より好ましくは前記有機アミンがメチルアミンである、項12に記載の方法。
項１４
前記式[A]
a
[M]
b
[X]
c
の化合物が、式[A][M][X]
3
(式中、[A]、[M]及び[X]が項1に定義されるとおりである)の化合物である、項1～13のいずれか一項に記載の方法。
項１５
[A]が少なくとも1つの有機カチオンを含む、項1～14のいずれか一項に記載の方法。
項１６
各Aカチオンが、アルカリ金属カチオン、式[R
1
R
2
R
3
R
4
N]
+
(式中、R
1
、R
2
、R
3
、R
4
はそれぞれ、独立して、水素、非置換又は置換C
1～20
アルキル、及び非置換又は置換C
6～12
アリールから選択され、R
1
、R
2
、R
3
及びR
4
のうちの少なくとも1つは水素ではない)のカチオン、式[R
5
R
6
N=CH-NR
7
R
8
]
+
(式中、R
5
、R
6
、R
7
及びR
8
はそれぞれ、独立して、水素、非置換又は置換C
1～20
アルキル、及び非置換又は置換C
6～12
アリールから選択される)のカチオン、並びにC
1～10
アルキルアンモニウム、C
2～10
アルケニルアンモニウム、C
1～10
アルキルイミニウム、C
3～10
シクロアルキルアンモニウム及びC
3～10
シクロアルキルイミニウム(これらは、それぞれ非置換又はアミノ、C
1～6
アルキルアミノ、イミノ、C
1～6
アルキルイミノ、C
1～6
アルキル、C
2～6
アルケニル、C
3～6
シクロアルキル及びC
6～12
アリールから選択される1つ以上の置換基で置換されている)から選択され、好ましくは各Aカチオンが、Cs
+
、Rb
+
、メチルアンモニウム、ジメチルアンモニウム、トリメチルアンモニウム、エチルアンモニウム、プロピルアンモニウム、ブチルアンモニウム、ペンチルアンモニウム、ヘキシルアンモニウム、ヘプチルアンモニウム、オクチルアンモニウム、テトラメチルアンモニウム、ホルムアミジニウム、1-アミノエタン-1-イミニウム及びグアニジニウムから選択される、前記項のいずれか一項に記載の方法。
項１７
[M]が2つ以上の異なるMカチオンを含む、項1～16のいずれか一項に記載の方法。
項１８
各Mカチオンが、Ca
2+
、Sr
2+
、Cd
2+
、Cu
2+
、Ni
2+
、Mn
2+
、Fe
2+
、Co
2+
、Pd
2+
、Ge
2+
、Sn
2+
、Pb
2+
、Yb
2+
及びEu
2+
、好ましくはSn
2+
、Pb
2+
、Cu
2+
、Ge
2+
及びNi
2+
、好ましくはSn
2+
及びPb
2+
から選択される、項1～17のいずれか一項に記載の方法。
項１９
各Xアニオンがハロゲン化物であり、任意選択で、[X]が2つ以上の異なるハロゲン化物アニオンを含む、項1～18のいずれか一項に記載の方法。
項２０
[A]が式[R
1
NH
3
]
+
(式中、R
1
は非置換C
1～10
アルキルである)のカチオンを含み、前記有機アミンが非置換(C
1～10
アルキル)アミンを含み、好ましくは式[R
1
NH
3
]
+
のAカチオン上のC
1～10
アルキル基及び非置換(C
1～10
アルキル)アミン上のC
1～10
アルキル基は同じであり、より好ましくは[A]がメチルアンモニウムを含み且つ前記有機アミンがメチルアミンを含む、項1～19のいずれか一項に記載の方法。
項２１
前記基材中の前記光活性領域中の前記光活性材料が、結晶A/M/X材料を含み、前記結晶A/M/X材料が、項1及び14～20のいずれか一項に定義される式[A]
a
[M]
b
[X]
c
の化合物を含む、項1～20のいずれか一項に記載の方法。
項２２
前記基材上に堆積された前記結晶A/M/X材料と前記光活性領域中の前記結晶A/M/X材料とが異なる、項21に記載の方法。
項２３
前記基材が2つの別々の光活性領域を含み、各光活性領域が光活性材料を含み、好ましくは各光活性領域中の各光活性材料が結晶A/M/X材料を含み、前記結晶A/M/X材料が、項1及び14～20のいずれか一項に定義される式[A]
a
[M]
b
[X]
c
の化合物を含み、任意選択で、前記基材上に堆積された前記結晶A/M/X材料及び前記2つの光活性領域中の前記結晶A/M/X材料から選択される結晶A/M/X材料の少なくとも2つが異なり、任意選択で、前記基材上に堆積された前記結晶A/M/X材料及び前記2つの光活性領域中の結晶A/M/X材料から選択される3つ全ての結晶A/M/X材料が異なる、項1～22のいずれか一項に記載の方法。
項２４
前記膜形成溶液が、1つ以上のAカチオン及び1つ以上のXアニオンをさらに含む、項1～23のいずれか一項に記載の方法。
項２５
1つ以上のAカチオン及び任意選択で1つ以上のXアニオンを含む組成物を前記基材上に配置する工程をさらに含む、項1～23のいずれか一項に記載の方法。
項２６
前記膜形成溶液を基材上に配置する工程が、前記膜形成溶液を前記基材上にスピンコーティングする工程を含む、項1～25のいずれか一項に記載の方法。
項２７
前記方法が、前記溶媒を除去して、前記結晶A/M/X材料を含む前記層を形成する工程をさらに含み、任意選択で、前記溶媒が、膜形成溶液で処理された基材を加熱することによって、任意選択で、膜形成溶液で処理された基材を50℃～200℃の温度で、任意選択で10～100分の時間の間、加熱することによって除去される、項1～26のいずれか一項に記載の方法。
項２８
前記基材が、
i)第1の電極、ここで、好ましくは前記第1の電極は、透明導電性酸化物を含む、
ii)光活性領域、ここで、前記光活性領域は、好ましくは結晶A/M/X材料を含み、前記結晶A/M/X材料は、項1及び14～20のいずれか一項に定義される式[A]
a
[M]
b
[X]
c
の化合物を含む、
iii)前記光活性領域上に配置された電荷再結合層、ここで、任意選択で、前記電荷再結合層は、項6～8のいずれか一項に定義されるとおりである、及び
iv)任意選択で、前記電荷再結合層上に配置された電荷輸送材料の層
を含む、項1～28のいずれか一項に記載の方法。
項２９
前記方法が、
第2の電極を前記基材上に配置された前記結晶A/M/X材料の前記層上に配置する工程、又は
好ましくは、電荷輸送材料を前記基材上に配置された前記結晶A/M/X材料の前記層上に配置し、第2の電極を前記電荷輸送材料上に配置する工程
をさらに含み、
好ましくは前記第2の電極が元素金属を含む、
項1～28のいずれか一項に記載の方法。
項３０
項1～29のいずれか一項に定義される方法により得ることができる多接合デバイス。
項３１
前記多接合デバイスが光電子デバイスであり、任意選択で、前記光電子デバイスが、光起電力デバイス又は発光デバイスである、項1～29のいずれか一項に記載の方法、又は項30に記載の多接合デバイス。
項３２
(a)少なくとも2つの光活性領域であって、前記光活性領域の少なくとも1つが結晶A/M/X材料の層を含み、前記結晶A/M/X材料が式[A]
a
[M]
b
[X]
c
(式中、[A]は1つ以上のAカチオンを含み、[M]は金属又は半金属のカチオンである1つ以上のMカチオンを含み、[X]は1つ以上のXアニオンを含み、aは1～6の数であり、bは1～6の数であり、cは1～18の数である)の化合物を含む、少なくとも2つの光活性領域、及び
(b)透明導電性酸化物のナノ粒子を含む電荷再結合層
を含む、多接合デバイス。
項３３
(a)少なくとも2つの光活性領域であって、前記光活性領域の少なくとも1つが結晶A/M/X材料の層を含み、前記結晶A/M/X材料が式[A]
a
[M]
b
[X]
c
(式中、[A]は1つ以上のAカチオンを含み、[M]は金属又は半金属のカチオンである1つ以上のMカチオンを含み、[X]は1つ以上のXアニオンを含み、aは1～6の数であり、bは1～6の数であり、cは1～18の数である)の化合物を含む、少なくとも2つの光活性領域、及び
(b)導電性ポリマーを含む電荷再結合層
を含む、多接合デバイス。
項３４
前記電荷再結合層が、透明導電性酸化物のナノ粒子及び導電性ポリマーを含み、任意選択で、前記電荷再結合層が、項6～8のいずれか一項にさらに定義されるとおりである、項32又は33に記載の多接合デバイス。
項３５
前記光活性領域のうちの2つが、項32又は33に定義される結晶A/M/X材料の層を含み、任意選択で、前記A/M/X材料が、項14～20のいずれか一項にさらに定義されるとおりである、項32～34のいずれか一項に記載の多接合デバイス。
項３６
少なくとも3つの光活性領域を含み、好ましくは各光活性領域が、項32又は33に定義される結晶A/M/X材料の層を含み、任意選択で、前記A/M/X材料が、項14～20のいずれか一項にさらに定義されるとおりである、項32～34のいずれか一項に記載の多接合デバイス。
項３７
(a)少なくとも3つの光活性領域であって、各光活性領域が、結晶A/M/X材料の層を含み、前記結晶A/M/X材料が式[A]
a
[M]
b
[X]
c
(式中、[A]は1つ以上のAカチオンを含み、[M]は金属又は半金属のカチオンである1つ以上のMカチオンを含み、[X]は1つ以上のXアニオンを含み、aは1～6の数であり、bは1～6の数であり、cは1～18の数である)の化合物を含む、少なくとも3つの光活性領域、及び
(b)前記光活性領域間に配置された少なくとも1つの電荷再結合層
を含む、多接合デバイス。
項３８
前記光活性領域間に配置された少なくとも2つの電荷再結合層を含む、項37に記載の多接合デバイス。
項３９
前記電荷再結合層の少なくとも1つが、導電性ポリマー又は透明導電性酸化物のナノ粒子を含む、項37又は38に記載の多接合デバイス。
項４０
前記電荷再結合層の少なくとも1つが、透明導電性酸化物のナノ粒子及び導電性ポリマーを含み、任意選択で、前記電荷再結合層の少なくとも1つが、項6～8のいずれか一項にさらに定義されるとおりである、項39に記載の多接合デバイス。
項４１
各光活性領域が、項14～20のいずれか一項にさらに定義される結晶A/M/X材料の層を含む、項32～40のいずれか一項に記載の多接合デバイス。
項４２
前記電荷再結合層の少なくとも1つが、(i)インジウムスズ酸化物(ITO)のナノ粒子並びに(ii)ポリ(3,4-エチレンジオキシチオフェン)及びポリスチレンスルホネートを含むポリマーを含む、項32～41のいずれか一項に記載の多接合デバイス。
項４３
前記結晶A/M/X材料の少なくとも2つが互いに異なり、任意選択で、前記結晶A/M/X材料の3つ以上が互いに異なる、項32～42のいずれか一項に記載の多接合デバイス。
項４４
第1の電極及び第2の電極をさらに含み、前記光活性領域及び前記電荷再結合層の少なくとも1つが、前記第1の電極及び前記第2の電極の間に配置され、好ましくは前記第1の電極が透明導電性酸化物を含み且つ前記第2の電極が元素金属を含む、項32～43のいずれか一項に記載の多接合デバイス。
項４５
光起電力デバイス又は発光デバイスである、項32～44のいずれか一項に記載の多接合デバイス。
Typically, the multijunction devices described herein include optoelectronic devices, photovoltaic devices, solar cells, photodetectors, photodiodes, photosensors, chromogenic devices, transistors, photosensitive transistors, photovoltaic devices. selected from the group consisting of transistors, solid state triodes, batteries, battery electrodes, capacitors, supercapacitors, light emitting devices, light emitting diodes and lasers. For example, the multijunction device may be an optoelectronic device. Examples of optoelectronic devices include photovoltaic devices, photodiodes (including solar cells), phototransistors, photomultipliers, photoresistors and light emitting devices. Preferably, the multijunction device is a photovoltaic device or a light emitting device.
Some embodiments are provided below.
Item 1
A method of fabricating a multijunction device comprising a layer of crystalline A/M/X material, wherein the crystalline A/M/X material has the formula [A] a [M] b [X] c
(In the formula,
[A] contains one or more A cations,
[M] includes one or more M cations that are metal or metalloid cations;
[X] contains one or more X anions,
a is a number from 1 to 6,
b is a number from 1 to 6,
c is a number from 1 to 18)
wherein the method comprises forming a layer of the crystalline A/M/X material by disposing a film-forming solution on a substrate, wherein the film-forming solution comprises
(a) one or more M cations, and
(b) solvent
wherein the solvent comprises
(i) an aprotic solvent, and
(ii) organic amines
wherein the substrate comprises
a photoactive region comprising a photoactive material; and
A charge recombination layer disposed over the photoactive region by solution deposition.
A method, including
Item 2
3. The method of paragraph 1, wherein the aprotic solvent is a polar aprotic solvent.
Item 3
3. The method of paragraphs 1 or 2, wherein the substrate further comprises a layer of charge transport material disposed on the charge recombination layer.
Item 4
disposing the charge recombination layer on the photoactive region by solution deposition;
optionally disposing a layer of charge transport material on said charge recombination layer;
Item 4. The method according to any one of Items 1 to 3, comprising a step of producing the base material by.
Item 5
The photoactive material in the substrate is soluble in dimethylformamide (DMF), dimethylsulfoxide (DMSO) or mixtures thereof, or at least one component of the charge recombination layer in the substrate is dimethyl dissolved in formamide (DMF), dimethylsulfoxide (DMSO) or mixtures thereof;
Preferably, both the photoactive material in the substrate and at least one component of the charge recombination layer in the substrate are in dimethylformamide (DMF), dimethylsulfoxide (DMSO) or mixtures thereof. dissolve,
More preferably, both the photoactive material in the substrate and the charge recombination layer in the substrate are soluble in dimethylformamide (DMF), dimethylsulfoxide (DMSO) or mixtures thereof. The method according to any one of 1-4.
Item 6
Clause 6. Clause 1-5, wherein the charge recombination layer comprises nanoparticles of a transparent conducting oxide, optionally wherein the transparent conducting oxide comprises indium tin oxide (ITO). Method.
Item 7
The nanoparticles of said transparent conductive oxide are disposed in a matrix material, such as an organic matrix material, optionally an electron-transporting organic matrix material, optionally wherein said organic matrix material comprises [6,6]-phenyl-C61 7. The method of paragraph 6, comprising -butyric acid methyl ester (PCBM).
Item 8
8. Item 6 or 7, wherein the charge recombination layer further comprises a conductive polymer, preferably the conductive polymer comprises poly(3,4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT:PSS). the method of.
Item 9
Disposing the charge recombination layer over the photoactive region comprises disposing a solvent dispersion of nanoparticles of a transparent conductive oxide over the photoactive region, preferably the charge recombination layer. over the photoactive region comprises disposing a conductive polymer over the photoactive region; and disposing a solvent dispersion of nanoparticles of a transparent conductive oxide over the photoactive region. optionally said solvent dispersion of nanoparticles further comprises a matrix material, e.g. an organic matrix material; optionally said solvent dispersion of nanoparticles and/or said conductive polymer is coated on said 9. The method of any one of clauses 4-8, disposed over a photoactive region.
Item 10
A method according to any one of paragraphs 1 to 9, wherein said aprotic solvent does not comprise dimethylformamide, preferably said aprotic solvent does not comprise dimethylformamide, dimethylsulfoxide or mixtures thereof.
Item 11
said aprotic solvent comprises a compound selected from the group consisting of chlorobenzene, acetone, butanone, methyl ethyl ketone, acetonitrile, propionitrile, toluene or mixtures thereof, preferably said aprotic solvent comprises acetonitrile, Clause 11. The method of any one of clauses 1-10.
Item 12
12. The method of any one of items 1-11, wherein the organic amine is an unsubstituted or substituted alkylamine or an unsubstituted or substituted arylamine.
Item 13
Said organic amine is an unsubstituted or substituted (C 1-10 alkyl) amine, preferably said organic amine is an unsubstituted (C 1-10 alkyl) amine or substituted with a phenyl group (C 1-10 alkyl ) amine, more preferably said organic amine is methylamine, ethylamine, propylamine, butylamine or pentylamine or hexylamine, benzylamine or phenylethylamine, more preferably said organic amine is methylamine. The method described in 12.
Item 14
The compound of formula [A] a [M] b [X] c is a compound of formula [A][M][X] 3 (wherein [A], [M] and [X] are 14. The method of any one of paragraphs 1-13, wherein the compound is a compound of
Item 15
15. The method of any one of paragraphs 1-14, wherein [A] comprises at least one organic cation.
Item 16
Each A cation is an alkali metal cation of the formula [R 1 R 2 R 3 R 4 N] + , where R 1 , R 2 , R 3 , R 4 are each independently hydrogen, unsubstituted or substituted C 1-20 alkyl, and unsubstituted or substituted C 6-12 aryl, wherein at least one of R 1 , R 2 , R 3 and R 4 is not hydrogen), a cation of the formula [R 5 R 6 N=CH-NR 7 R 8 ] + (wherein R 5 , R 6 , R 7 and R 8 are each independently hydrogen, unsubstituted or substituted C 1-20 alkyl, and unsubstituted or substituted cations selected from C 6-12 aryl) and C 1-10 alkylammonium, C 2-10 alkenylammonium, C 1-10 alkyliminium, C 3-10 cycloalkylammonium and C 3-10 cycloalkyl iminium (which are respectively unsubstituted or amino, C 1-6 alkylamino, imino, C 1-6 alkylimino, C 1-6 alkyl, C 2-6 alkenyl, C 3-6 cycloalkyl and C 6- 12 aryl substituted with one or more substituents selected from aryl), preferably each A cation is Cs + , Rb + , methylammonium, dimethylammonium, trimethylammonium, ethylammonium, propylammonium, A method according to any one of the preceding clauses, selected from butylammonium, pentylammonium, hexylammonium, heptylammonium, octylammonium, tetramethylammonium, formamidinium, 1-aminoethane-1-iminium and guanidinium.
Item 17
17. The method of any one of paragraphs 1-16, wherein [M] comprises two or more different M cations.
Item 18
Each M cation is Ca 2+ , Sr 2+ , Cd 2+ , Cu 2+ , Ni 2+ , Mn 2+ , Fe 2+ , Co 2+ , Pd 2+ , Ge 2+ , Sn 2+ , Pb 2+ , Yb 2+ and Eu 2+ , preferably Sn 2+ , Pb 2+ , Cu 2+ , Ge 2+ and Ni 2+ , preferably Sn 2+ and Pb 2+ , items 1 to 18. The method of any one of 17.
Item 19
19. The method of any one of clauses 1-18, wherein each X anion is a halide and optionally [X] comprises two or more different halide anions.
Item 20
[A] comprises a cation of the formula [R 1 NH 3 ] + where R 1 is unsubstituted C 1-10 alkyl and said organic amine comprises an unsubstituted (C 1-10 alkyl) amine; , preferably the C 1-10 alkyl group on the A cation of the formula [R 1 NH 3 ] + and the C 1-10 alkyl group on the unsubstituted (C 1-10 alkyl)amine are the same, more preferably [ A] comprises methylammonium and said organic amine comprises methylamine.
Item 21
The photoactive material in the photoactive region in the substrate comprises a crystalline A/M/X material, wherein the crystalline A/M/X material is defined in any one of paragraphs 1 and 14-20. 21. The method of any one of clauses 1-20, comprising a compound of formula [A] a [M] b [X] c wherein
Item 22
22. The method of paragraph 21, wherein the crystalline A/M/X material deposited on the substrate and the crystalline A/M/X material in the photoactive region are different.
Item 23
said substrate comprising two separate photoactive regions, each photoactive region comprising a photoactive material, preferably each photoactive material in each photoactive region comprising a crystalline A/M/X material, said crystalline A/M/X material comprising a compound of formula [A] a [M] b [X] c as defined in any one of paragraphs 1 and 14-20, optionally on said substrate at least two of the deposited crystalline A/M/X material and the crystalline A/M/X material selected from the crystalline A/M/X material in the two photoactive regions are different; All three crystalline A/M/X materials selected from said crystalline A/M/X material deposited on a substrate and said crystalline A/M/X materials in said two photoactive regions are different. 23. The method of any one of 1-22.
Item 24
24. The method of any one of paragraphs 1-23, wherein the film-forming solution further comprises one or more A cations and one or more X anions.
Item 25
24. The method of any one of clauses 1-23, further comprising the step of disposing a composition comprising one or more A cations and optionally one or more X anions on said substrate.
Item 26
26. The method of any one of clauses 1-25, wherein disposing the film-forming solution on a substrate comprises spin-coating the film-forming solution onto the substrate.
Item 27
The method further comprises removing the solvent to form the layer comprising the crystalline A/M/X material, optionally wherein the solvent heats the substrate treated with the film-forming solution. is optionally removed by heating the substrate treated with the film forming solution at a temperature of 50° C. to 200° C., optionally for a period of 10 to 100 minutes, sections 1- 27. The method of any one of paragraphs 26.
Item 28
The base material is
i) a first electrode, wherein preferably said first electrode comprises a transparent conductive oxide,
ii) a photoactive region, wherein said photoactive region preferably comprises a crystalline A/M/X material, said crystalline A/M/X material as defined in any one of paragraphs 1 and 14-20; comprising a compound of the formula [A] a [M] b [X] c
iii) a charge recombination layer disposed over said photoactive region, wherein optionally said charge recombination layer is as defined in any one of paragraphs 6 to 8; and
iv) optionally a layer of charge transport material disposed on said charge recombination layer
29. The method of any one of paragraphs 1-28, comprising:
Item 29
said method comprising:
disposing a second electrode on said layer of said crystalline A/M/X material disposed on said substrate, or
Preferably, a charge transport material is disposed on said layer of said crystalline A/M/X material disposed on said substrate and a second electrode is disposed on said charge transport material.
further comprising
preferably said second electrode comprises an elemental metal,
Clause 29. The method of any one of clauses 1-28.
Item 30
A multijunction device obtainable by a method as defined in any one of paragraphs 1-29.
Item 31
31. The method of any one of clauses 1 to 29, or the multijunction device of clause 30, wherein the multijunction device is an optoelectronic device, optionally wherein the optoelectronic device is a photovoltaic device or a light emitting device. junction device.
Item 32
(a) at least two photoactive regions, at least one of said photoactive regions comprising a layer of crystalline A/M/X material, said crystalline A/M/X material having the formula [A] a [M] b [X] c (where [A] contains one or more A cations, [M] contains one or more M cations that are metal or metalloid cations, and [X] is one or more a is a number from 1 to 6, b is a number from 1 to 6, and c is a number from 1 to 18), and
(b) a charge recombination layer containing nanoparticles of transparent conductive oxides;
A multijunction device comprising:
Item 33
(a) at least two photoactive regions, at least one of said photoactive regions comprising a layer of crystalline A/M/X material, said crystalline A/M/X material having the formula [A] a [M] b [X] c (where [A] contains one or more A cations, [M] contains one or more M cations that are metal or metalloid cations, and [X] is one or more a is a number from 1 to 6, b is a number from 1 to 6, and c is a number from 1 to 18), and
(b) a charge recombination layer comprising a conductive polymer;
A multijunction device comprising:
Item 34
wherein said charge recombination layer comprises transparent conductive oxide nanoparticles and a conductive polymer; optionally said charge recombination layer is as further defined in any one of paragraphs 6-8. 34. A multijunction device according to paragraph 32 or 33.
Item 35
Two of said photoactive regions comprise a layer of crystalline A/M/X material as defined in paragraphs 32 or 33, and optionally said A/M/X material is any of paragraphs 14-20. 35. The multijunction device of any one of clauses 32-34, as further defined in clause 32-34.
Item 36
comprising at least three photoactive regions, preferably each photoactive region comprising a layer of crystalline A/M/X material as defined in paragraph 32 or 33, optionally said A/M/X material comprising: 35. The multijunction device of any one of clauses 32-34, as further defined in any one of clauses 14-20.
Item 37
(a) at least three photoactive regions, each photoactive region comprising a layer of crystalline A/M/X material, said crystalline A/M/X material having the formula [A] a [M] b [ X] c (wherein [A] contains one or more A cations, [M] contains one or more M cations that are metal or metalloid cations, [X] contains one or more X an anion, a is a number from 1 to 6, b is a number from 1 to 6, and c is a number from 1 to 18);
(b) at least one charge recombination layer disposed between said photoactive regions;
A multijunction device comprising:
Item 38
38. The multijunction device of Paragraph 37, comprising at least two charge recombination layers disposed between said photoactive regions.
Item 39
39. The multijunction device of paragraphs 37 or 38, wherein at least one of said charge recombination layers comprises nanoparticles of a conducting polymer or a transparent conducting oxide.
Item 40
At least one of said charge recombination layers comprises transparent conductive oxide nanoparticles and a conductive polymer; optionally at least one of said charge recombination layers further comprises 40. The multijunction device of Paragraph 39, as defined.
Item 41
41. The multijunction device of any one of Clauses 32-40, wherein each photoactive region comprises a layer of crystalline A/M/X material as further defined in any one of Clauses 14-20.
Item 42
Sections 32-, wherein at least one of the charge recombination layers comprises (i) nanoparticles of indium tin oxide (ITO) and (ii) a polymer comprising poly(3,4-ethylenedioxythiophene) and polystyrene sulfonate. 42. The multijunction device of any one of 41.
Item 43
43. The multijunction device of any one of clauses 32-42, wherein at least two of said crystalline A/M/X materials are different from each other, and optionally three or more of said crystalline A/M/X materials are different from each other. .
Item 44
Further comprising a first electrode and a second electrode, wherein at least one of said photoactive region and said charge recombination layer is disposed between said first electrode and said second electrode, preferably said first electrode. 44. The multijunction device of any one of clauses 32-43, wherein the electrode of comprises a transparent conductive oxide and said second electrode comprises an elemental metal.
Item 45
45. The multijunction device of any one of paragraphs 32-44, which is a photovoltaic device or a light emitting device.
Claims (17)
結晶A/M/X材料が式[A]a[M]b[X]c
(式中、
[A]は、1つ以上のAカチオンを含み、
[M]は、金属又は半金属のカチオンである1つ以上のMカチオンを含み、
[X]は、1つ以上のXアニオンを含み、
aは1～6の数であり、
bは1～6の数であり、
cは1～18の数である)
の化合物を含み、
前記方法が、膜形成溶液を基材上に配置することにより前記結晶A/M/X材料の層を形成する工程を含み、
ここで、前記膜形成溶液は、
(a)1つ以上のMカチオン、及び
(b)溶媒
を含み、
前記溶媒は、
(i)非プロトン性溶媒、及び
(ii)有機アミン
を含み、
前記基材は、
光活性材料を含む光活性領域、及び
溶液堆積法により前記光活性領域上に配置される電荷再結合層
を含む、方法。 A method of manufacturing a multijunction device comprising layers of crystalline A/M/X material, comprising:
A crystalline A/M/X material has the formula [A] a [M] b [X] c
(In the formula,
[A] contains one or more A cations,
[M] includes one or more M cations that are metal or metalloid cations;
[X] contains one or more X anions,
a is a number from 1 to 6,
b is a number from 1 to 6,
c is a number from 1 to 18)
containing compounds of
said method comprising forming a layer of said crystalline A/M/X material by disposing a film-forming solution on a substrate;
Here, the film-forming solution is
(a) one or more M cations, and
(b) contains a solvent;
The solvent is
(i) an aprotic solvent, and
(ii) contains an organic amine;
The base material is
A method comprising: a photoactive region comprising a photoactive material; and a charge recombination layer disposed over the photoactive region by solution deposition.
任意選択で、電荷輸送材料の層を前記電荷再結合層上に配置する工程
により、前記基材を製造する工程を含む、請求項1又は請求項2に記載の方法。 disposing the charge recombination layer on the photoactive region by a solution deposition method; and optionally disposing a layer of charge transport material on the charge recombination layer. 3. The method of claim 1 or claim 2 , comprising
好ましくは、前記基材中の前記光活性材料と前記基材中の前記電荷再結合層の少なくとも1つの成分との両方が、ジメチルホルムアミド(DMF)、ジメチルスルホキシド(DMSO)又はこれらの混合物中に溶解し、
より好ましくは、前記基材中の前記光活性材料と前記基材中の前記電荷再結合層との両方が、ジメチルホルムアミド(DMF)、ジメチルスルホキシド(DMSO)又はこれらの混合物中に溶解し、及び/又は
(B)前記電荷再結合層が透明導電性酸化物のナノ粒子を含み、任意選択で、前記透明導電性酸化物がインジウムスズ酸化物(ITO)を含み、任意選択で、
前記透明導電性酸化物のナノ粒子がマトリックス材料、例えば有機マトリックス材料、任意選択で、電子輸送有機マトリックス材料中に配置され、任意選択で、前記有機マトリックス材料が[6,6]-フェニル-C61-酪酸メチルエステル(PCBM)を含み、任意選択で、
前記電荷再結合層が導電性ポリマーをさらに含み、好ましくは、前記導電性ポリマーが、ポリ(3,4-エチレンジオキシチオフェン)及びポリスチレンスルホネート(PEDOT:PSS)を含む、請求項1～3のいずれか一項に記載の方法。 (A) the photoactive material in the substrate is soluble in dimethylformamide (DMF), dimethylsulfoxide (DMSO) or mixtures thereof, or at least one component of the charge recombination layer in the substrate; is dissolved in dimethylformamide (DMF), dimethylsulfoxide (DMSO) or mixtures thereof,
Preferably, both the photoactive material in the substrate and at least one component of the charge recombination layer in the substrate are in dimethylformamide (DMF), dimethylsulfoxide (DMSO) or mixtures thereof. dissolve,
More preferably, both the photoactive material in the substrate and the charge recombination layer in the substrate are dissolved in dimethylformamide (DMF), dimethylsulfoxide (DMSO) or mixtures thereof, and / or
(B) the charge recombination layer comprises nanoparticles of a transparent conductive oxide, optionally wherein the transparent conductive oxide comprises indium tin oxide (ITO);
The nanoparticles of said transparent conductive oxide are disposed in a matrix material, such as an organic matrix material, optionally an electron-transporting organic matrix material, optionally wherein said organic matrix material comprises [6,6]-phenyl-C61 - containing butyric acid methyl ester (PCBM), optionally
of claims 1-3, wherein the charge recombination layer further comprises a conductive polymer, preferably the conductive polymer comprises poly(3,4-ethylenedioxythiophene) and polystyrene sulfonate (PEDOT:PSS). A method according to any one of paragraphs.
前記非プロトン性溶媒が、クロロベンゼン、アセトン、ブタノン、メチルエチルケトン、アセトニトリル、プロピオニトリル、トルエン又はこれらの混合物からなる群から選択される化合物を含み、好ましくは、前記非プロトン性溶媒がアセトニトリルを含む、及び/又は
前記有機アミンが、非置換若しくは置換アルキルアミン又は非置換若しくは置換アリールアミンであり、任意選択で、
前記有機アミンが非置換又は置換(C 1～10 アルキル)アミンであり、好ましくは前記有機アミンが、非置換(C 1～10 アルキル)アミン又はフェニル基で置換されている(C 1～10 アルキル)アミンであり、より好ましくは前記有機アミンが、メチルアミン、エチルアミン、プロピルアミン、ブチルアミン若しくはペンチルアミン若しくはヘキシルアミン、ベンジルアミン又はフェニルエチルアミンであり、より好ましくは前記有機アミンがメチルアミンである、請求項1～5のいずれか一項に記載の方法。 said aprotic solvent does not comprise dimethylformamide, preferably said aprotic solvent does not comprise dimethylformamide, dimethylsulfoxide or mixtures thereof, and/or
said aprotic solvent comprises a compound selected from the group consisting of chlorobenzene, acetone, butanone, methyl ethyl ketone, acetonitrile, propionitrile, toluene or mixtures thereof, preferably said aprotic solvent comprises acetonitrile, and/or
said organic amine is an unsubstituted or substituted alkylamine or an unsubstituted or substituted arylamine, optionally
Said organic amine is an unsubstituted or substituted (C 1-10 alkyl) amine, preferably said organic amine is an unsubstituted (C 1-10 alkyl) amine or substituted with a phenyl group (C 1-10 alkyl ) amine, more preferably said organic amine is methylamine, ethylamine, propylamine, butylamine or pentylamine or hexylamine, benzylamine or phenylethylamine, more preferably said organic amine is methylamine. 6. The method of any one of paragraphs 1-5.
[A]が少なくとも1つの有機カチオンを含む、及び/又は
各Aカチオンが、アルカリ金属カチオン、式[R 1 R 2 R 3 R 4 N] + (式中、R 1 、R 2 、R 3 、R 4 はそれぞれ、独立して、水素、非置換又は置換C 1～20 アルキル、及び非置換又は置換C 6～12 アリールから選択され、R 1 、R 2 、R 3 及びR 4 のうちの少なくとも1つは水素ではない)のカチオン、式[R 5 R 6 N=CH-NR 7 R 8 ] + (式中、R 5 、R 6 、R 7 及びR 8 はそれぞれ、独立して、水素、非置換又は置換C 1～20 アルキル、及び非置換又は置換C 6～12 アリールから選択される)のカチオン、並びにC 1～10 アルキルアンモニウム、C 2～10 アルケニルアンモニウム、C 1～10 アルキルイミニウム、C 3～10 シクロアルキルアンモニウム及びC 3～10 シクロアルキルイミニウム(これらは、それぞれ非置換又はアミノ、C 1～6 アルキルアミノ、イミノ、C 1～6 アルキルイミノ、C 1～6 アルキル、C 2～6 アルケニル、C 3～6 シクロアルキル及びC 6～12 アリールから選択される1つ以上の置換基で置換されている)から選択され、好ましくは各Aカチオンが、Cs + 、Rb + 、メチルアンモニウム、ジメチルアンモニウム、トリメチルアンモニウム、エチルアンモニウム、プロピルアンモニウム、ブチルアンモニウム、ペンチルアンモニウム、ヘキシルアンモニウム、ヘプチルアンモニウム、オクチルアンモニウム、テトラメチルアンモニウム、ホルムアミジニウム、1-アミノエタン-1-イミニウム及びグアニジニウムから選択される、及び/又は
[M]が2つ以上の異なるMカチオンを含む、及び/又は
各Mカチオンが、Ca 2+ 、Sr 2+ 、Cd 2+ 、Cu 2+ 、Ni 2+ 、Mn 2+ 、Fe 2+ 、Co 2+ 、Pd 2+ 、Ge 2+ 、Sn 2+ 、Pb 2+ 、Yb 2+ 及びEu 2+ 、好ましくはSn 2+ 、Pb 2+ 、Cu 2+ 、Ge 2+ 及びNi 2+ 、好ましくはSn 2+ 及びPb 2+ から選択される、及び/又は
各Xアニオンがハロゲン化物であり、任意選択で、[X]が2つ以上の異なるハロゲン化物アニオンを含む、及び/又は
[A]が式[R 1 NH 3 ] + (式中、R 1 は非置換C 1～10 アルキルである)のカチオンを含み、前記有機アミンが非置換(C 1～10 アルキル)アミンを含み、好ましくは式[R 1 NH 3 ] + のAカチオン上のC 1～10 アルキル基及び非置換(C 1～10 アルキル)アミン上のC 1～10 アルキル基は同じであり、より好ましくは[A]がメチルアンモニウムを含み且つ前記有機アミンがメチルアミンを含む、請求項1～6のいずれか一項に記載の方法。 The compound of formula [A] a [M] b [X] c is a compound of formula [A][M][X] 3 (where [A], [M] and [X] are and/or
[A] contains at least one organic cation, and/or
Each A cation is an alkali metal cation of the formula [R 1 R 2 R 3 R 4 N] + , where R 1 , R 2 , R 3 , R 4 are each independently hydrogen, unsubstituted or substituted C 1-20 alkyl, and unsubstituted or substituted C 6-12 aryl, wherein at least one of R 1 , R 2 , R 3 and R 4 is not hydrogen), a cation of the formula [R 5 R 6 N=CH-NR 7 R 8 ] + (wherein R 5 , R 6 , R 7 and R 8 are each independently hydrogen, unsubstituted or substituted C 1-20 alkyl, and unsubstituted or substituted cations selected from C 6-12 aryl) and C 1-10 alkylammonium, C 2-10 alkenylammonium, C 1-10 alkyliminium, C 3-10 cycloalkylammonium and C 3-10 cycloalkyl iminium (which are respectively unsubstituted or amino, C 1-6 alkylamino, imino, C 1-6 alkylimino, C 1-6 alkyl, C 2-6 alkenyl, C 3-6 cycloalkyl and C 6- 12 aryl substituted with one or more substituents selected from aryl), preferably each A cation is Cs + , Rb + , methylammonium, dimethylammonium, trimethylammonium, ethylammonium, propylammonium, selected from butylammonium, pentylammonium, hexylammonium, heptylammonium, octylammonium, tetramethylammonium, formamidinium, 1-aminoethane-1-iminium and guanidinium; and/or
[M] contains two or more different M cations, and/or
Each M cation is Ca 2+ , Sr 2+ , Cd 2+ , Cu 2+ , Ni 2+ , Mn 2+ , Fe 2+ , Co 2+ , Pd 2+ , Ge 2+ , Sn 2+ , Pb 2+ , Yb 2+ and Eu 2+ , preferably Sn 2+ , Pb 2+ , Cu 2+ , Ge 2+ and Ni 2+ , preferably Sn 2+ and Pb 2+ and/or
each X anion is a halide, optionally [X] comprises two or more different halide anions, and/or
[A] comprises a cation of the formula [R 1 NH 3 ] + where R 1 is unsubstituted C 1-10 alkyl and said organic amine comprises an unsubstituted (C 1-10 alkyl) amine; , preferably the C 1-10 alkyl group on the A cation of the formula [R 1 NH 3 ] + and the C 1-10 alkyl group on the unsubstituted (C 1-10 alkyl)amine are the same, more preferably [ A] comprises methylammonium and said organic amine comprises methylamine.
前記基材上に堆積された前記結晶A/M/X材料と前記光活性領域中の前記結晶A/M/X材料とが異なる、及び/又は
前記基材が2つの別々の光活性領域を含み、各光活性領域が光活性材料を含み、好ましくは各光活性領域中の各光活性材料が結晶A/M/X材料を含み、前記結晶A/M/X材料が、請求項1又は請求項7に定義される式[A] a [M] b [X] c の化合物を含み、任意選択で、前記基材上に堆積された前記結晶A/M/X材料及び前記2つの光活性領域中の前記結晶A/M/X材料から選択される結晶A/M/X材料の少なくとも2つが異なり、任意選択で、前記基材上に堆積された前記結晶A/M/X材料及び前記2つの光活性領域中の結晶A/M/X材料から選択される3つ全ての結晶A/M/X材料が異なる、及び/又は
前記膜形成溶液が、1つ以上のAカチオン及び1つ以上のXアニオンをさらに含む、及び/又は
前記方法が、1つ以上のAカチオン及び任意選択で1つ以上のXアニオンを含む組成物を前記基材上に配置する工程をさらに含む、及び/又は
前記膜形成溶液を基材上に配置する工程が、前記膜形成溶液を前記基材上にスピンコーティングする工程を含む、及び/又は
前記方法が、前記溶媒を除去して、前記結晶A/M/X材料を含む前記層を形成する工程をさらに含み、任意選択で、前記溶媒が、膜形成溶液で処理された基材を加熱することによって、任意選択で、膜形成溶液で処理された基材を50℃～200℃の温度で、任意選択で10～100分の時間の間、加熱することによって除去される、請求項1～7のいずれか一項に記載の方法。 The photoactive material in the photoactive region in the substrate comprises a crystalline A/M/X material, the crystalline A/M/X material having the formula defined in claim 1 or claim 7 [ A] a [M] b [X] c optionally comprising
the crystalline A/M/X material deposited on the substrate and the crystalline A/M/X material in the photoactive region are different, and/or
said substrate comprising two separate photoactive regions, each photoactive region comprising a photoactive material, preferably each photoactive material in each photoactive region comprising a crystalline A/M/X material, said crystalline A/M/X material comprising a compound of the formula [A] a [M] b [X] c as defined in claim 1 or claim 7, and optionally said at least two of the crystalline A/M/X materials and the crystalline A/M/X materials selected from the crystalline A/M/X materials in the two photoactive regions are different, optionally on the substrate all three crystalline A/M/X materials selected from the deposited crystalline A/M/X material and the crystalline A/M/X materials in the two photoactive regions are different; and/or
the film-forming solution further comprises one or more A cations and one or more X anions, and/or
the method further comprises disposing a composition comprising one or more A cations and optionally one or more X anions on the substrate; and/or
disposing the film-forming solution on a substrate comprises spin-coating the film-forming solution onto the substrate; and/or
The method further comprises removing the solvent to form the layer comprising the crystalline A/M/X material, optionally wherein the solvent heats the substrate treated with the film-forming solution. optionally removed by heating the substrate treated with the film-forming solution at a temperature of 50° C. to 200° C., optionally for a period of 10 to 100 minutes. 8. The method according to any one of 7.
i)第1の電極、ここで、好ましくは前記第1の電極は、透明導電性酸化物を含む、
ii)光活性領域、ここで、前記光活性領域は、好ましくは結晶A/M/X材料を含み、前記結晶A/M/X材料は、請求項1又は請求項7に定義される式[A]a[M]b[X]cの化合物を含む、
iii)前記光活性領域上に配置された電荷再結合層、ここで、任意選択で、前記電荷再結合層は、請求項4に定義されるとおりである、及び
iv)任意選択で、前記電荷再結合層上に配置された電荷輸送材料の層
を含む、及び/又は
(B)前記方法が、
第2の電極を前記基材上に配置された前記結晶A/M/X材料の前記層上に配置する工程、又は
好ましくは、電荷輸送材料を前記基材上に配置された前記結晶A/M/X材料の前記層上に配置し、第2の電極を前記電荷輸送材料上に配置する工程
をさらに含み、
好ましくは前記第2の電極が元素金属を含む、
請求項1～8のいずれか一項に記載の方法。 (A) the substrate is
i) a first electrode, wherein preferably said first electrode comprises a transparent conductive oxide,
ii) a photoactive region, wherein said photoactive region preferably comprises a crystalline A/M/X material, said crystalline A/M/X material having the formula as defined in claim 1 or claim 7 A] a [M] b [X] c compounds,
iii) a charge recombination layer disposed over the photoactive region, wherein optionally the charge recombination layer is as defined in claim 4 , and
iv) optionally comprising a layer of charge transport material disposed on said charge recombination layer, and/or
(B) the method is
disposing a second electrode on said layer of said crystalline A/M/X material disposed on said substrate, or
Preferably, a charge transport material is disposed on said layer of said crystalline A/M/X material disposed on said substrate and a second electrode is disposed on said charge transport material.
further comprising
preferably said second electrode comprises an elemental metal,
A method according to any one of claims 1-8.
(b)透明導電性酸化物のナノ粒子を含む電荷再結合層
を含む、多接合デバイス。 (a) at least two photoactive regions, at least one of said photoactive regions comprising a layer of crystalline A/M/X material, said crystalline A/M/X material having the formula [A] a [M] b [X] c (where [A] contains one or more A cations, [M] contains one or more M cations that are metal or metalloid cations, and [X] is one or more a is a number from 1 to 6, b is a number from 1 to 6, and c is a number from 1 to 18), and
(b) a multi-junction device comprising a charge recombination layer comprising nanoparticles of transparent conductive oxides;
(b)導電性ポリマーを含む電荷再結合層
を含む、多接合デバイス。 (a) at least two photoactive regions, at least one of said photoactive regions comprising a layer of crystalline A/M/X material, said crystalline A/M/X material having the formula [A] a [M] b [X] c (where [A] contains one or more A cations, [M] contains one or more M cations that are metal or metalloid cations, and [X] is one or more a is a number from 1 to 6, b is a number from 1 to 6, and c is a number from 1 to 18), and
(b) a multijunction device comprising a charge recombination layer comprising a conducting polymer;
前記光活性領域のうちの2つが、請求項12又は13に定義される結晶A/M/X材料の層を含み、任意選択で、前記A/M/X材料が、請求項7にさらに定義されるとおりである、及び/又は
前記多接合デバイスが、少なくとも3つの光活性領域を含み、好ましくは各光活性領域が、請求項12又は13に定義される結晶A/M/X材料の層を含み、任意選択で、前記A/M/X材料が、請求項7にさらに定義されるとおりである、請求項12又は請求項13に記載の多接合デバイス。 wherein said charge recombination layer comprises transparent conductive oxide nanoparticles and a conductive polymer, optionally said charge recombination layer is as further defined in claim 4 ; and/or
Two of said photoactive regions comprise a layer of crystalline A/M/X material as defined in claim 12 or 13, optionally said A/M/X material further defined in claim 7. and/or
The multijunction device comprises at least three photoactive regions, preferably each photoactive region comprising a layer of crystalline A/M/X material as defined in claim 12 or 13, optionally wherein the A 14. The multijunction device of claim 12 or claim 13, wherein the /M/X material is as further defined in claim 7.
(b)前記光活性領域間に配置された少なくとも1つの電荷再結合層
を含む、多接合デバイス。 (a) at least three photoactive regions, each photoactive region comprising a layer of crystalline A/M/X material, said crystalline A/M/X material having the formula [A] a [M] b [ X] c (wherein [A] contains one or more A cations, [M] contains one or more M cations that are metal or metalloid cations, [X] contains one or more X an anion, a is a number from 1 to 6, b is a number from 1 to 6, and c is a number from 1 to 18);
(b) a multijunction device comprising at least one charge recombination layer disposed between said photoactive regions;
前記電荷再結合層の少なくとも1つが、導電性ポリマー又は透明導電性酸化物のナノ粒子を含む、及び/又は
前記電荷再結合層の少なくとも1つが、透明導電性酸化物のナノ粒子及び導電性ポリマーを含み、任意選択で、前記電荷再結合層の少なくとも1つが、請求項4にさらに定義されるとおりである、請求項15に記載の多接合デバイス。 the multijunction device includes at least two charge recombination layers disposed between the photoactive regions; and/or
at least one of the charge recombination layers comprises nanoparticles of a conducting polymer or a transparent conducting oxide; and/or
At least one of said charge recombination layers comprises transparent conductive oxide nanoparticles and a conductive polymer, optionally at least one of said charge recombination layers is as further defined in claim 4 16. The multijunction device of claim 15 .
前記電荷再結合層の少なくとも1つが、(i)インジウムスズ酸化物(ITO)のナノ粒子並びに(ii)ポリ(3,4-エチレンジオキシチオフェン)及びポリスチレンスルホネートを含むポリマーを含む、及び/又は
前記結晶A/M/X材料の少なくとも2つが互いに異なり、任意選択で、前記結晶A/M/X材料の3つ以上が互いに異なる、及び/又は
前記多接合デバイスが第1の電極及び第2の電極をさらに含み、前記光活性領域及び前記電荷再結合層の少なくとも1つが、前記第1の電極及び前記第2の電極の間に配置され、好ましくは前記第1の電極が透明導電性酸化物を含み且つ前記第2の電極が元素金属を含む、及び/又は
前記多接合デバイスが光起電力デバイス又は発光デバイスである、請求項12～16のいずれか一項に記載の多接合デバイス。 each photoactive region comprises a layer of crystalline A/M/X material as further defined in claim 7 , and/or
at least one of the charge recombination layers comprises (i) nanoparticles of indium tin oxide (ITO) and (ii) a polymer comprising poly(3,4-ethylenedioxythiophene) and polystyrene sulfonate; and/or
at least two of said crystalline A/M/X materials are different from each other, optionally three or more of said crystalline A/M/X materials are different from each other, and/or
said multijunction device further comprising a first electrode and a second electrode, wherein at least one of said photoactive region and said charge recombination layer is disposed between said first electrode and said second electrode; preferably said first electrode comprises a transparent conductive oxide and said second electrode comprises an elemental metal, and/or
17. The multijunction device of any one of claims 12-16, wherein the multijunction device is a photovoltaic device or a light emitting device.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB1817166.0 | 2018-10-22 | ||
| GBGB1817166.0A GB201817166D0 (en) | 2018-10-22 | 2018-10-22 | Multi-junction device production process |
| PCT/GB2019/052988 WO2020084285A1 (en) | 2018-10-22 | 2019-10-18 | Multi-junction device production process |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JP2022505477A JP2022505477A (en) | 2022-01-14 |
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| CN110783459A (en) * | 2019-10-31 | 2020-02-11 | 深圳市华星光电半导体显示技术有限公司 | Film layer manufacturing method and light-emitting device |
| CN111382508B (en) * | 2020-03-04 | 2024-04-26 | 西安理工大学 | Design method of physical visualization simulation platform of semiconductor device based on data model |
| US20210388009A1 (en) * | 2020-06-10 | 2021-12-16 | Nanyang Technological University | Organic metal-halide perovskite precursor, process for production and use thereof |
| CN111816774B (en) * | 2020-07-17 | 2022-08-16 | 南京理工大学 | Visible/infrared spectrum switchable double-frequency detection imaging perovskite device |
| CN112670423A (en) * | 2020-12-21 | 2021-04-16 | 南京大学 | Perovskite light emitting diode capable of emitting white light, preparation method thereof and light emitting device |
| WO2022183239A1 (en) * | 2021-03-04 | 2022-09-09 | Commonwealth Scientific And Industrial Research Organisation | A process of forming an electrode interconnection in an integrated multilayer thin-film electronic device |
| CN116426164A (en) * | 2023-04-08 | 2023-07-14 | 上海应用技术大学 | Anti-counterfeiting application of copper-based perovskite material with water-based color change |
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| GB201604050D0 (en) | 2016-03-09 | 2016-04-20 | Isis Innovation | A/M/X material production process with alkylamine |
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