Method of fabricating an organic photodiode with dual electron blocking layers

Patent metadata

Field	Value
Publication number	US-9960353-B2
Application number	US-201615338801-A
Country	US
Kind code	B2
Filing date	Oct 31, 2016
Priority date	Aug 28, 2013
Publication date	May 1, 2018
Grant date	May 1, 2018

Abstract

Embodiments of forming an image sensor with an organic photodiode are provided. The organic photodiode uses dual electron-blocking layers formed next to the anode of the organic photodiode to reduce dark current. By using dual electron-blocking layers, the values of highest occupied molecular orbital (HOMO) for the neighboring anode layer and the organic electron-blocking layer are matched by one of the dual electron-blocking layers to form a photodiode with good performance. The values of the lowest occupied molecular orbital (LOMOs) of the dual electron-blocking layers are selected to be lower than the neighboring anode layer to reduce dark current.

First claim

What is claimed is:

1. A method of forming an organic photodiode, comprising:
forming a first electrode layer;
depositing by physical vapor deposition (PVD) a first electron-blocking layer of V 2 O 5 over the first electrode layer;
depositing a second electron-blocking layer using PVD over the first electron-blocking layer, wherein the second electron-blocking layer includes MoO 3 , wherein the second electron-blocking layer is deposited having a first thickness and the first electron-blocking layer is deposited having a second thickness, the first thickness less than the second thickness;
forming an organic P-type layer over the second electron-blocking layer;
forming an organic active layer over the organic P-type layer;
forming an organic N-type layer over the organic active layer;
forming a hole-blocking layer over the organic N-type layer; and
forming a second electrode layer over the hole-blocking layer.

2. The method of claim 1 , wherein the organic active layer formed is a blend of materials used to form the organic hole-transport layer and the organic electron-transport layer, wherein the blend forms bulk heterojunction.

3. The method of claim 1 , wherein the second thickness is about 10 nm and the first thickness is about 2 nm.

4. The method of claim 1 , further comprising:
selecting a composition of the first electrode layer having a first work function material such that a highest occupied molecular orbital (HOMO) value of the first electron-blocking layer is substantially equal to that of the first work function material.

5. The method of claim 1 , further comprising:
selecting a composition of the second electrode layer having a second work function material, such that a lowest occupied molecular orbital (LOMO) value of the hole-blocking layer is substantially equal to that of the second work function material.

6. The method of claim 1 , further comprising;
selecting a composition of the organic P-type layer having a first value of highest occupied molecular orbital (HOMO); and
selecting a composition of the second electron-blocking layer having a second value of HOMO, the first and second HOMO values having a difference of less than approximately 0.4 eV.

7. A method of fabricating an organic photodiode, comprising:
providing a first electrode layer having a first work function;
depositing using physical vapor deposition a first electron-blocking layer over the first electrode layer, wherein the first electron-blocking layer has a first value of highest occupied molecular orbital (HOMO), wherein the first value of HOMO is substantially equal to the first work function;
depositing using physical vapor deposition a second electron-blocking layer of MoO 3 directly over the first electron-blocking layer, wherein the second electron-blocking layer includes a metal-oxide having a second value of HOMO, and wherein the second electron-blocking layer is thinner than the first electron-blocking layer;
depositing a plurality of organic layers over the first and second electron-blocking layers; and
forming a second electrode layer over the plurality of organic layers, wherein a lowest occupied molecular orbital (LOMO) value of at least one of the plurality of organic layers is substantially equal to the LOMO value of the second electrode layer.

8. The method of claim 7 , wherein the depositing the plurality of organic layers includes depositing at least one of: thiophene-based conjugated polymer, such as poly(3-hyxylthiophene) (P3HT), benzodithiophene-based conjugated polymer, thieno[3,4-c]pyrrole-4,6-dione (TPD)-based conjugated polymer, diketo-pyrrole-pyrrole (DPP)-based conjugated polymer, bithiazole (BTz)-based conjugated polymers, benzothiadiazole (BT)-based conjugated polymer, and thieno[3,2-b]thiophene (TT)-based conjugated polymer.

9. The method of claim 7 , wherein at least one of the plurality of organic layers is deposited by mixing a conjugated polymer and aromatic solvent to form a mixture;
spaying with a nozzle on a surface of the second electron-blocking layer.

10. The method of claim 9 , further comprising: stirring the mixture at an elevated temperature prior to the spraying.

11. The method of claim 7 , wherein the first electron-blocking layer comprises V 2 O 5 .

12. The method of claim 7 , further comprising:
depositing a hole-blocking layer prior to the forming the second electrode layer;
wherein the hole-blocking layer comprises a transparent material.

13. A method of fabricating an organic photodiode, comprising:
providing a first electrode layer having a first work function;
depositing a first electron-blocking layer by physical vapor deposition of V 2 O 5 directly on the first electrode, wherein the first electron-blocking layer over the first electrode layer, wherein the first electrode layer has a first value of highest occupied molecular orbital (HOMO), wherein the first value of HOMO is substantially equal to the first work function;
depositing a second electron-blocking layer directly over the first electron-blocking layer, wherein the second electron-blocking layer includes a metal-oxide having a second value of HOMO different than the first, and wherein the second electron-blocking layer is thinner than the first electron-blocking layer;
depositing a plurality of organic layers over the first and second electron-blocking layers;
forming a second electrode layer over the plurality of organic layers;
forming a photoresist layer over the second electrode layer;
using the photoresist layer as a masking element in an etching process, wherein the etching process includes etching the first electrode layer, the first electron-blocking layer, the second electron-blocking layer, the plurality of organic layers, and the second electrode layer to form an opening; and
filling the opening with a light-blocking structure.

14. The method of claim 13 , wherein the depositing the second electron-blocking layer includes depositing by physical vapor deposition MoO 3.

15. The method of claim 13 , wherein the depositing a plurality of organic layers includes:
forming an organic P-type layer over the second electron-blocking layer;
forming an organic active layer over the organic P-type layer;
forming an organic N-type layer over the organic active layer.

16. The method of claim 15 , further comprising:
depositing a hole-blocking layer over the organic N-type layer prior to forming the second electrode layer, wherein the second electrode layer is deposited directly on the hole-blocking layer.

17. The method of claim 1 , wherein the first thickness is approximately 2 nanometers (nm) and the second thickness is approximately 10 nanometers (nm).

18. The method of claim 1 , wherein the forming the hole-blocking layer over the organic N-type layer includes depositing a composition for the hole-blocking layer having a lower occupied molecular orbital (LOMO) that is equal the LOMO of a composition of the second electrode layer.

Assignees

• Taiwan Semiconductor Mfg Co Ltd

Inventors

• Liang Chin-Wei
• Lin Hsing-Lien
• Tsai Cheng-Yuan
• Tsai Chia-Shiung

Classifications

• H01L51/0035

  Electricity · mapped topic

• H01L51/002 Primary

  Electricity · mapped topic

• H01L51/4253

  Electricity · mapped topic

• Y02E10/549

  Organic PV cells · CPC title

• H01L51/0036

  Electricity · mapped topic