JPWO2016208326A1 - 光電変換素子、撮像素子、積層型撮像素子及び撮像装置 - Google Patents
光電変換素子、撮像素子、積層型撮像素子及び撮像装置 Download PDFInfo
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- JPWO2016208326A1 JPWO2016208326A1 JP2017524780A JP2017524780A JPWO2016208326A1 JP WO2016208326 A1 JPWO2016208326 A1 JP WO2016208326A1 JP 2017524780 A JP2017524780 A JP 2017524780A JP 2017524780 A JP2017524780 A JP 2017524780A JP WO2016208326 A1 JPWO2016208326 A1 JP WO2016208326A1
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- 229910052716 thallium Inorganic materials 0.000 description 1
- BKVIYDNLLOSFOA-UHFFFAOYSA-N thallium Chemical compound [Tl] BKVIYDNLLOSFOA-UHFFFAOYSA-N 0.000 description 1
- 150000003557 thiazoles Chemical class 0.000 description 1
- JOUDBUYBGJYFFP-FOCLMDBBSA-N thioindigo Chemical class S\1C2=CC=CC=C2C(=O)C/1=C1/C(=O)C2=CC=CC=C2S1 JOUDBUYBGJYFFP-FOCLMDBBSA-N 0.000 description 1
- 150000003573 thiols Chemical class 0.000 description 1
- ANRHNWWPFJCPAZ-UHFFFAOYSA-M thionine Chemical class [Cl-].C1=CC(N)=CC2=[S+]C3=CC(N)=CC=C3N=C21 ANRHNWWPFJCPAZ-UHFFFAOYSA-M 0.000 description 1
- 150000003577 thiophenes Chemical class 0.000 description 1
- 150000004882 thiopyrans Chemical class 0.000 description 1
- 150000005075 thioxanthenes Chemical class 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 1
- 125000005628 tolylene group Chemical group 0.000 description 1
- TVIVIEFSHFOWTE-UHFFFAOYSA-K tri(quinolin-8-yloxy)alumane Chemical compound [Al+3].C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1.C1=CN=C2C([O-])=CC=CC2=C1 TVIVIEFSHFOWTE-UHFFFAOYSA-K 0.000 description 1
- VPYJNCGUESNPMV-UHFFFAOYSA-N triallylamine Chemical class C=CCN(CC=C)CC=C VPYJNCGUESNPMV-UHFFFAOYSA-N 0.000 description 1
- 150000005109 triphenodioxazines Chemical class 0.000 description 1
- 125000005580 triphenylene group Chemical group 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 229910052721 tungsten Inorganic materials 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
- 238000004506 ultrasonic cleaning Methods 0.000 description 1
- 238000001771 vacuum deposition Methods 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
- 125000001834 xanthenyl group Chemical class C1=CC=CC=2OC3=CC=CC=C3C(C12)* 0.000 description 1
- NAWDYIZEMPQZHO-UHFFFAOYSA-N ytterbium Chemical compound [Yb] NAWDYIZEMPQZHO-UHFFFAOYSA-N 0.000 description 1
- YVTHLONGBIQYBO-UHFFFAOYSA-N zinc indium(3+) oxygen(2-) Chemical compound [O--].[Zn++].[In+3] YVTHLONGBIQYBO-UHFFFAOYSA-N 0.000 description 1
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Abstract
Description
V =Q/C
で表され、結局、有機撮像素子の電気容量が大きくなると、Vが小さくなり、その結果、電気信号が小さくなってしまう。尚、有機撮像素子の電気容量(具体的には、次に述べる有機層の電気容量)は、電気容量の総量Cの約半分を占めている。また、一般に、電気容量C0は、誘電率をε、面積をS0、厚さをd0としたとき、
C0=(ε・S0)/d0
で表されるため、有機撮像素子の低容量化を左右する因子として、画素面積、有機撮像素子を構成する材料の誘電率、有機撮像素子における有機層の厚さが挙げられる。そして、厚さによって低容量化を図る場合には、有機撮像素子の有機層の総膜厚を厚くする必要がある。
キャリアブロッキング層は、下記の構造式(1)を有する材料、及び、有機光電変換層を構成する有機半導体材料の一部から成る。
1.本開示の光電変換素子、本開示の撮像素子、本開示の積層型撮像素子、本開示の第1の態様〜第2の態様に係る撮像装置、全般に関する説明
2.実施例1(本開示の光電変換素子、本開示の撮像素子、本開示の第1の態様に係る撮像装置)
3.実施例2(実施例1の変形、本開示の積層型撮像素子、本開示の第2の態様に係る撮像装置)
4.その他
本開示の積層型撮像素子において、具体的には、青色の光(425nm乃至495nmの光)を吸収する有機光電変換層を備えた青色に感度を有する本開示の撮像素子(便宜上、『青色用撮像素子』と呼ぶ)、緑色の光(495nm乃至570nmの光)を吸収する有機光電変換層を備えた緑色に感度を有する本開示の撮像素子(便宜上、『緑色用撮像素子』と呼ぶ)、赤色の光(620nm乃至750nmの光)を吸収する有機光電変換層を備えた赤色に感度を有する本開示の撮像素子(便宜上、『赤色用撮像素子』と呼ぶ)の3つの撮像素子が、垂直方向に積層された構成を挙げることができる。尚、これらの撮像素子の積層順は、光入射方向から青色用撮像素子、緑色用撮像素子、赤色用撮像素子の順、あるいは、光入射方向から緑色用撮像素子、青色用撮像素子、赤色用撮像素子の順であることが好ましい。これは、より短い波長の光がより入射表面側において効率良く吸収されるからである。赤色は3色の中では最も長い波長であるので、光入射面から見て赤色用撮像素子を最下層に位置させることが好ましい。あるいは又、シリコン半導体基板に赤色に感度を有する撮像素子を形成し、シリコン半導体基板の上に緑色用撮像素子、青色用撮像素子を形成する構成とすることもできるし、シリコン半導体基板に2種類の撮像素子を形成し、シリコン半導体基板の上に1種類の本開示の撮像素子を形成する構成とすることもできる。シリコン半導体基板に形成された撮像素子は、裏面照射型であることが好ましいが、表面照射型とすることもできる。光電変換層を構成する無機系材料として、結晶シリコン以外にも、アモルファスシリコン、微結晶シリコン、結晶セレン、アモルファスセレン、及び、カルコパライト系化合物であるCIGS(CuInGaSe)、CIS(CuInSe2)、CuInS2、CuAlS2、CuAlSe2、CuGaS2、CuGaSe2、AgAlS2、AgAlSe2、AgInS2、AgInSe2、あるいは又、III−V族化合物であるGaAs、InP、AlGaAs、InGaP、AlGaInP、InGaAsP、更には、CdSe、CdS、In2Se3、In2S3、Bi2Se3、Bi2S3、ZnSe、ZnS、PbSe、PbS等の化合物半導体を挙げることができる。加えて、これらの材料から成る量子ドットを無機光電変換層に使用することも可能である。また、本開示の第1の態様〜第2の態様に係る撮像装置によって、単板式カラー撮像装置を構成することができる。
(1)単層又は複数層から成るp型有機半導体層から構成する。
(2)p型有機半導体層/n型有機半導体層の積層構造から構成する。p型有機半導体層/p型有機半導体とn型有機半導体との混合層(バルクヘテロ構造)/n型有機半導体層の積層構造から構成する。p型有機半導体層/p型有機半導体とn型有機半導体との混合層(バルクヘテロ構造)の積層構造から構成する。n型有機半導体層/p型有機半導体とn型有機半導体との混合層(バルクヘテロ構造)の積層構造から構成する。
(3)p型有機半導体とn型有機半導体の混合(バルクヘテロ構造)から構成する。
の3態様のいずれかとすることができる。尚、バルクヘテロ構造には、2種類の半導体材料だけでなく、3種類以上の半導体材料も含まれる。
λ1/2 =500nm
λ-1/2=590nm
であり、光電変換材料層の光吸収スペクトルは、波長450nm乃至650nmの範囲において1つの極大値を有していた。
実施例1の撮像素子(光電変換素子)において、厚さ5nmの陽極側バッファ層を成膜し、次いで、実施例1とは異なり、陽極側キャリアブロッキング層を形成することなく、厚さ10nmのQD層、厚さ120nmのQD:Cl層、厚さ5nmの陰極側バッファ層、厚さ0.5nmのフッ化リチウム層、厚さ60nmの陰極を成膜することで、比較例1Aの評価用の撮像素子(光電変換素子)を得た。
実施例1の撮像素子(光電変換素子)において、厚さ5nmの陽極側バッファ層を成膜し、次いで、実施例1とは異なり、厚さ100nmの構造式(1)を有する層(陽極側キャリアブロッキング層)を形成し、構造式(1)を有する材料とキナクリドンとから成る陽極側キャリアブロッキング層を形成することなく、厚さ10nmのQD層、厚さ120nmのQD:Cl層、厚さ5nmの陰極側バッファ層、厚さ0.5nmのフッ化リチウム層、厚さ60nmの陰極を成膜することで、比較例1Bの評価用の撮像素子(光電変換素子)を得た。
実施例1の撮像素子(光電変換素子)において、厚さ5nmの陽極側バッファ層を成膜し、次いで、実施例1とは異なり、陽極側キャリアブロッキング層として、以下の構造式(5)を有する厚さ50nmの材料層、並びに、厚さ20nmの以下の構造式(5)を有する材料及びキナクリドンから成る層を形成し、更に、厚さ10nmのQD層、厚さ120nmのQD:Cl層、厚さ5nmの陰極側バッファ層、厚さ0.5nmのフッ化リチウム層、厚さ60nmの陰極を成膜することで、比較例1Cの評価用の撮像素子(光電変換素子)を得た。
[A01]《撮像素子》
少なくとも、陽極、キャリアブロッキング層、有機光電変換層、陰極が、順次、積層されて成る撮像素子であって、
キャリアブロッキング層は、下記の構造式(1)を有する材料、及び、有機光電変換層を構成する有機半導体材料の一部から成る撮像素子。
[A02]有機光電変換層を構成する有機半導体材料の一部はキナクリドン又はキナクリドン誘導体から成る[A01]に記載の撮像素子。
[A03]キャリアブロッキング層は、構造式(1)を有する材料及び有機光電変換層を構成する有機半導体材料の一部から成る層と、構造式(1)を有する材料から成る層との積層構造から構成されている[A01]又は[A02]に記載の撮像素子。
[A04]陽極及び陰極は透明導電材料から成る[A01]乃至[A03]のいずれか1項に記載の撮像素子。
[A05]陽極及び陰極のいずれか一方は透明導電材料から成り、他方は金属材料から成る[A01]乃至[A03]のいずれか1項に記載の撮像素子。
[A06]陽極は透明導電材料から成り、陰極は、Al、Al−Si−Cu又はMg−Agから成る[A05]に記載の撮像素子。
[A07]陰極は透明導電材料から成り、陽極は、Al−Nd又はASCから成る[A05]に記載の撮像素子。
[B01]《積層型撮像素子》
[A01]乃至[A07]のいずれか1項に記載の撮像素子が、少なくとも2つ、積層されて成る積層型撮像素子。
[C01]《撮像装置:第1の態様》
[A01]乃至[A07]のいずれか1項に記載の撮像素子を、複数、備えた撮像装置。
[C02]《撮像装置:第2の態様》
[B01]に記載の積層型撮像素子を、複数、備えた撮像装置。
[D01]《光電変換素子》
少なくとも、陽極、キャリアブロッキング層、有機光電変換層、陰極が、順次、積層されて成る撮像素子であって、
キャリアブロッキング層は、下記の構造式(1)を有する材料、及び、有機光電変換層を構成する有機半導体材料の一部から成る光電変換素子。
Claims (11)
- 少なくとも、陽極、キャリアブロッキング層、有機光電変換層、陰極が、順次、積層されて成る撮像素子であって、
キャリアブロッキング層は、下記の構造式(1)を有する材料、及び、有機光電変換層を構成する有機半導体材料の一部から成る撮像素子。
- 有機光電変換層を構成する有機半導体材料の一部はキナクリドン又はキナクリドン誘導体から成る請求項1に記載の撮像素子。
- キャリアブロッキング層は、構造式(1)を有する材料及び有機光電変換層を構成する有機半導体材料の一部から成る層と、構造式(1)を有する材料から成る層との積層構造から構成されている請求項1に記載の撮像素子。
- 陽極及び陰極は透明導電材料から成る請求項1に記載の撮像素子。
- 陽極及び陰極のいずれか一方は透明導電材料から成り、他方は金属材料から成る請求項1に記載の撮像素子。
- 陽極は透明導電材料から成り、陰極は、Al、Al−Si−Cu又はMg−Agから成る請求項5に記載の撮像素子。
- 陰極は透明導電材料から成り、陽極は、Al−Nd又はASCから成る請求項5に記載の撮像素子。
- 請求項1乃至請求項7のいずれか1項に記載の撮像素子が、少なくとも2つ、積層されて成る積層型撮像素子。
- 請求項1乃至請求項7のいずれか1項に記載の撮像素子を、複数、備えた撮像装置。
- 請求項8に記載の積層型撮像素子を、複数、備えた撮像装置。
- 少なくとも、陽極、キャリアブロッキング層、有機光電変換層、陰極が、順次、積層されて成る撮像素子であって、
キャリアブロッキング層は、下記の構造式(1)を有する材料、及び、有機光電変換層を構成する有機半導体材料の一部から成る光電変換素子。
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JP2011228630A (ja) * | 2010-03-31 | 2011-11-10 | Fujifilm Corp | 撮像素子及びその製造方法 |
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JP2011228630A (ja) * | 2010-03-31 | 2011-11-10 | Fujifilm Corp | 撮像素子及びその製造方法 |
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