JPS6247169A - Photosensor - Google Patents

Photosensor

Info

Publication number
JPS6247169A
JPS6247169A JP60186897A JP18689785A JPS6247169A JP S6247169 A JPS6247169 A JP S6247169A JP 60186897 A JP60186897 A JP 60186897A JP 18689785 A JP18689785 A JP 18689785A JP S6247169 A JPS6247169 A JP S6247169A
Authority
JP
Japan
Prior art keywords
light
optical sensor
electrode
organic semiconductor
wavelength
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
JP60186897A
Other languages
Japanese (ja)
Other versions
JPH0587033B2 (en
Inventor
Katsuaki Umibe
海部 勝晶
Yoichi Nishioka
洋一 西岡
Masakazu Kato
雅一 加藤
Kazutami Kawamura
川村 和民
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Oki Electric Industry Co Ltd
Original Assignee
Oki Electric Industry Co Ltd
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Oki Electric Industry Co Ltd filed Critical Oki Electric Industry Co Ltd
Priority to JP60186897A priority Critical patent/JPS6247169A/en
Publication of JPS6247169A publication Critical patent/JPS6247169A/en
Publication of JPH0587033B2 publication Critical patent/JPH0587033B2/ja
Granted legal-status Critical Current

Links

Classifications

    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K85/00Organic materials used in the body or electrodes of devices covered by this subclass
    • H10K85/30Coordination compounds
    • H10K85/311Phthalocyanine
    • HELECTRICITY
    • H10SEMICONDUCTOR DEVICES; ELECTRIC SOLID-STATE DEVICES NOT OTHERWISE PROVIDED FOR
    • H10KORGANIC ELECTRIC SOLID-STATE DEVICES
    • H10K39/00Integrated devices, or assemblies of multiple devices, comprising at least one organic radiation-sensitive element covered by group H10K30/00
    • H10K39/30Devices controlled by radiation
    • YGENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02EREDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00Energy generation through renewable energy sources
    • Y02E10/50Photovoltaic [PV] energy
    • Y02E10/549Organic PV cells

Landscapes

  • Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Photovoltaic Devices (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Electroluminescent Light Sources (AREA)
  • Nitrogen Condensed Heterocyclic Rings (AREA)
  • Light Receiving Elements (AREA)

Abstract

(57)【要約】本公報は電子出願前の出願データであるた
め要約のデータは記録されません。
(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

【発明の詳細な説明】 (産業上の利用分野) この発明は、有機半導体を用いた光センサ、特に、近赤
外光領域の波長600〜11000nの光に対して高感
度な光センサに関する。
DETAILED DESCRIPTION OF THE INVENTION (Field of Industrial Application) The present invention relates to an optical sensor using an organic semiconductor, and particularly to an optical sensor that is highly sensitive to light in the near-infrared region with a wavelength of 600 to 11,000 nm.

(従来の技術) 従来よりシリコン等の無機半導体のp−n接合を用いて
太陽電池やイメージセンサ等の光センサが実用化されて
いる。
(Prior Art) Conventionally, optical sensors such as solar cells and image sensors have been put into practical use using pn junctions of inorganic semiconductors such as silicon.

一方、ある種の有機化合物は半導体の性質を示すことが
知られている。このような有機化合物は有機半導体と称
され、この有機半導体を用いた種々の光センサが提案さ
れている。この有機半導体を用いれば可撓性を必要とす
るセンサの実現が可能であり、又、大面積なセンサが作
製出来ること、さらに、この有機半導体は材料コストが
安くかつ加工が容易なため、低価格なセンサが作製出来
ること等の理由で、多方面への応用が期待出来る。
On the other hand, it is known that certain organic compounds exhibit semiconductor properties. Such organic compounds are called organic semiconductors, and various optical sensors using these organic semiconductors have been proposed. By using this organic semiconductor, it is possible to realize a sensor that requires flexibility, and it is also possible to fabricate a sensor with a large area.Furthermore, this organic semiconductor has low material cost and is easy to process, so it is possible to realize a sensor that requires flexibility. Because it is possible to produce inexpensive sensors, it can be expected to be applied in many fields.

このような有機半導体を用いた光センサは、例えば文献
(アプライド フィジックス レターズ(Applie
d Physics Letters ) 38 (2
) (1981) P。
Optical sensors using such organic semiconductors are described, for example, in the literature (Applied Physics Letters).
d Physics Letters) 38 (2
) (1981) P.

85〜86)に開示されている。この光センサは、メロ
シアニン色素とアルミニウムとのショットキー接合を利
用したものであり、その構造は、絶縁性下地としてのポ
リエステルフィルム上に、第一電極としてのITO透明
電極膜が形成されていて、この第一電極−にに、真空蒸
着法により、メロシアニン色素からなる有機半導体層が
形成され、さらに、この有機半導体層−1二には第二電
極としてのアルミニウム電極が形成された構造である。
85-86). This optical sensor utilizes a Schottky junction between a merocyanine dye and aluminum, and its structure includes an ITO transparent electrode film as a first electrode formed on a polyester film as an insulating base. An organic semiconductor layer made of merocyanine dye is formed on this first electrode by a vacuum evaporation method, and an aluminum electrode as a second electrode is further formed on this organic semiconductor layer 12.

このメロシアニン色素の構造式を下記(II )に示す
The structural formula of this merocyanine dye is shown in (II) below.

又、この光センサの光電流スペクトルを、縦軸に光電流
を任意スケールでとり、横軸に光センサに照射される光
の波長をとり、光の波長に対する光電流をプロットして
第4図に示す。このメロシアニン色素を有機半導体層と
して構成した光センサは400〜600nmの波長の光
に対して優れた感度を示す。
In addition, the photocurrent spectrum of this optical sensor is plotted by plotting the photocurrent against the wavelength of light by plotting the photocurrent on the vertical axis at an arbitrary scale and the wavelength of the light irradiated on the optical sensor on the horizontal axis, as shown in Figure 4. Shown below. An optical sensor comprising this merocyanine dye as an organic semiconductor layer exhibits excellent sensitivity to light with a wavelength of 400 to 600 nm.

(発明が解決しようとする問題点) しかしながら、従来の有機半導体を用いた光センサでは
近赤外線領域での感度に優れた光センサが得られなかっ
たため、近赤外線領域では有機半導体を用いた光センサ
を使用出来ないという問題点があった。一方、高出力で
高安定というような良好な特性を有する発光素子の開発
は、光通信の光ファイバを低損失とすることが出来る波
長帯である、近赤外領域で発光する素子を中心として行
われている。従って、有機半導体を用いた光センサが有
する、可撓性と、大面積のものが製作可能なこと、低価
格化が可能なこと等の特性を生かした、近赤外領域で高
感度な有機半導体を用いた光センサの開発が望まれてい
た。
(Problem to be solved by the invention) However, since conventional optical sensors using organic semiconductors have not been able to provide optical sensors with excellent sensitivity in the near-infrared region, optical sensors using organic semiconductors have There was a problem that it was not possible to use . On the other hand, the development of light-emitting devices with good characteristics such as high output and high stability has focused on devices that emit light in the near-infrared region, which is the wavelength band that allows optical fibers for optical communication to have low loss. It is being done. Therefore, we have developed an organic optical sensor with high sensitivity in the near-infrared region that takes advantage of the characteristics of optical sensors using organic semiconductors, such as flexibility, the ability to manufacture large-area products, and the ability to reduce costs. The development of optical sensors using semiconductors has been desired.

この発明の目的は、近赤外領域において広帯域に高感度
な特性を有する有機半導体を用いた光センサを提供する
ことにある。
An object of the present invention is to provide an optical sensor using an organic semiconductor having characteristics of high sensitivity over a wide band in the near-infrared region.

(問題点を解決するための手段) この目的の達成を図るため、この発明によれば、光電変
換層として有機半導体層を用し)だ光センサにおいて、 この有機半導体層を下記の構造式(m)で表わされるク
ロロインジウムナフタロシアニンとしたことを特徴とす
る。
(Means for solving the problem) In order to achieve this object, according to the present invention, in an optical sensor using an organic semiconductor layer as a photoelectric conversion layer, the organic semiconductor layer is formed by the following structural formula ( It is characterized by being a chloroindium naphthalocyanine represented by m).

(作用) このような構成によれば、クロロインジウムナフタロシ
アニンは、波−1600〜11000nの光を吸収する
性質を有しているから、この波長領域の光を吸収するこ
とにより、クロロインジウムナフタロシアニン層の電子
がエネルギー的に高い状態に励起される。又、電子が抜
けた跡には正孔が生ずる。このように、電子会正孔対が
形成されるため光電変換が起こり、第一電極と第二電極
との間に電圧が生じる。従って、近赤外光領域の600
〜11000nの波長の光に対して高感度な光センサ素
子を得ることが出来る。
(Function) According to such a configuration, since chloroindium naphthalocyanine has the property of absorbing light in the wavelength range of −1600 to 11000 nm, by absorbing light in this wavelength range, chloroindium naphthalocyanine Electrons in the layer are excited to a higher energy state. In addition, holes are generated in the place where the electrons left. In this way, photoelectric conversion occurs because electron-hole pairs are formed, and a voltage is generated between the first electrode and the second electrode. Therefore, 600 in the near-infrared region
A photosensor element that is highly sensitive to light with a wavelength of ~11,000 nm can be obtained.

(実施例) 以下、図面を参照してこの発明の一実施例につき説明す
る。
(Embodiment) Hereinafter, one embodiment of the present invention will be described with reference to the drawings.

尚1これらの図はこの発明が理解出来る程度に概略的に
示しであるにすぎず、各構成成分の寸法、形状及び配置
関係は図示例に限定されるものではない。
Note that these drawings are only schematic representations to the extent that the present invention can be understood, and the dimensions, shapes, and arrangement relationships of each component are not limited to the illustrated examples.

第1図は、この発明の光センサの構造の−実施例を示す
断面図ある。
FIG. 1 is a sectional view showing an embodiment of the structure of an optical sensor according to the present invention.

第1図において、11は絶縁性下地とし例えばガラス基
板を示す。このガラス基板11上に、蒸着法等の好適な
方法により、第一電極13として例えばITO透明電極
が設けられている。さらに、この透明電極13 J〕に
、蒸着法により有機半導体層15として下記構造式(I
V)で表わされるクロロインジウムナフタロシアニン薄
膜が0.1gmの膜厚で設けらており、さらに、この有
機半導体層15上に第二電極17として例えばアルミニ
ウム背面電極が設けられている。
In FIG. 1, reference numeral 11 indicates an insulating base, for example, a glass substrate. For example, an ITO transparent electrode is provided as the first electrode 13 on the glass substrate 11 by a suitable method such as vapor deposition. Furthermore, an organic semiconductor layer 15 of the following structural formula (I
A chloroindium naphthalocyanine thin film represented by V) is provided with a thickness of 0.1 gm, and furthermore, an aluminum back electrode, for example, is provided as a second electrode 17 on this organic semiconductor layer 15.

このように構成された光センサに、ガラス基板11側か
ら、50 pLW/ c m2の光強度で、かつ、波長
を600〜11000nの範囲で変化させて、単色光を
照射する。この時、ガラス基板11及び透明電極13を
透過したこの単色光が、有機半導体層15に吸収されて
起こる光電変換により透明電極13と背面電極17との
間に発生する電圧(以下、開放端電圧と称する)を測定
した。第2図は、縦軸に電圧をとり、横軸に波長をとり
、光センサに照射した光の波長に対する、両電極間に発
生する開放端電圧をプロットして示した特性曲線図であ
る。第2図からも明らかなように、クロロインジウムナ
フタロシアニン薄膜の光吸収スペクトルに対応した、近
赤外線領域の600〜11000nの波長の光に対して
、透明電極13と背面電極17との間に1mV以上の開
放端電圧が発生した。
The thus configured optical sensor is irradiated with monochromatic light from the glass substrate 11 side at a light intensity of 50 pLW/cm 2 and with the wavelength varied in the range of 600 to 11000 nm. At this time, this monochromatic light transmitted through the glass substrate 11 and the transparent electrode 13 is absorbed by the organic semiconductor layer 15, and a voltage (hereinafter referred to as open-end voltage) is generated between the transparent electrode 13 and the back electrode 17 due to photoelectric conversion that occurs. ) was measured. FIG. 2 is a characteristic curve diagram in which the voltage is plotted on the vertical axis and the wavelength is plotted on the horizontal axis, and the open end voltage generated between both electrodes is plotted against the wavelength of light irradiated onto the optical sensor. As is clear from FIG. 2, 1 mV is applied between the transparent electrode 13 and the back electrode 17 for light with a wavelength of 600 to 11,000 nm in the near-infrared region, which corresponds to the light absorption spectrum of the chloroindium naphthalocyanine thin film. An open circuit voltage of more than 10% was generated.

次に、この光センサに、そのガラス基板11側から、波
長を870nmと固定した光で、その光強度を0.1〜
200pW/cm2 の範囲で変化させて、光を照射す
る。この時透明電極13と背面電極17との間に発生す
る開放端電圧を測定する。第3図は、縦軸に電圧をとり
、横軸に光強度をとり、光センサに照射する光の強度に
対する開放端電圧をプロットして示した特性曲線図であ
る。開放端電圧は光強度に比例して変化することがわか
った。
Next, light with a fixed wavelength of 870 nm is applied to this optical sensor from the glass substrate 11 side, and the light intensity is set to 0.1 to 870 nm.
Light is irradiated while changing the power within a range of 200 pW/cm2. At this time, the open end voltage generated between the transparent electrode 13 and the back electrode 17 is measured. FIG. 3 is a characteristic curve diagram in which the vertical axis represents voltage and the horizontal axis represents light intensity, and the open end voltage is plotted against the intensity of light irradiated onto the optical sensor. It was found that the open circuit voltage changes in proportion to the light intensity.

尚、−」二連した実施例においては、クロロインジウム
ナフタロシアニンの膜厚を0.1pmとして光センサを
作製したが、この膜厚は実施例の膜厚に限定されるもの
ではなく、光センサに要求される特性に応じた所望の膜
厚とすることが出来る。
In addition, in the two consecutive examples, the optical sensor was produced with a film thickness of chloroindium naphthalocyanine of 0.1 pm, but this film thickness is not limited to the film thickness of the example, and the optical sensor The desired film thickness can be set according to the characteristics required.

又、上述した実施例において、絶縁性下地をガラス基板
としたが、他の材料例えばポリエステルフィルムのよう
な可撓性を有する下地としても良い。又、第一電極とし
た透明電極と、第二電極としたアルミニウム配面電極と
を入換えて、透明電極側から光照射をするように光セン
サを構成すれば、絶縁性下地は、特に透明な材質でなく
とも良い。
Further, in the above-described embodiments, the insulating base is a glass substrate, but other materials may be used, such as a flexible base such as a polyester film. In addition, if the transparent electrode used as the first electrode and the aluminum plated electrode used as the second electrode are exchanged and the optical sensor is configured so that light is irradiated from the transparent electrode side, the insulating base is particularly transparent. It doesn't have to be made of the same material.

又、アルミニウムで構成した背面電極を、例えば、イン
ジウム又はマグネシウム等としても良い。
Furthermore, the back electrode made of aluminum may be made of, for example, indium or magnesium.

(発明の効果) 上述した説明からも明らかなように、この発明によれば
、有機半導体を用いた光センサにおいて、有機半導体層
をクロロインジウムナフタロシアニンとしである。
(Effects of the Invention) As is clear from the above description, according to the present invention, in the optical sensor using an organic semiconductor, the organic semiconductor layer is made of chloroindium naphthalocyanine.

こノクロロインジウムナフタロシアニンは、波長600
〜11000nの光を吸収する性質を有しているから、
この波長領域の光を吸収する。
This nochloroindium naphthalocyanine has a wavelength of 600
Because it has the property of absorbing light of ~11000n,
It absorbs light in this wavelength range.

従って、この光吸収により有機半導体層で光電変換が起
こり、第一電極と第二電極との間に電圧が生じる。
Therefore, photoelectric conversion occurs in the organic semiconductor layer due to this light absorption, and a voltage is generated between the first electrode and the second electrode.

これがため、近赤外光領域の600〜 11000nの波長の光に対して高感度な光センサ素子
を提供することが出来る。
Therefore, it is possible to provide a photosensor element that is highly sensitive to light having a wavelength of 600 to 11,000 nm in the near-infrared light region.

従って、この発明の光センサを用いれば、近赤外領域で
使用出来、可撓性を有し、大面桔で、かつ、低価格なイ
メージセンサ等が実現出来る。
Therefore, by using the optical sensor of the present invention, it is possible to realize an image sensor that can be used in the near-infrared region, has flexibility, has a large surface area, and is inexpensive.

【図面の簡単な説明】[Brief explanation of drawings]

第1図はこの発明の光センサの一実施例を示す断面図、 第2図はこの発明の光センサの光波長に対する光電変換
特性を示す特性曲線図、 第3図はこの発明の光センサの一定波長での光強度に対
する光電変換特性を示す特性曲線図、第4図は従来の光
センサの説明に供する線図である。 11・・・絶縁性下地(ガラス基板) 13・・・第一電極(ITO透明電極)15・・・有機
半導体層(クロロインジウムナフタロシアニン) 17・・・第二電極(アルミニウム背面電極)。 特許出願人    沖電気工業株式会社ll°昶1壷を
生下文亡(カ゛う入基才及)13゛茅−償利ν (工丁
O祷り月(極ン/ご「 号1m:手導づシト・7勺; 17:第二を1ケ(γ]し5ニアA嘴9動1&)この全
6月の光せ〉プの噌め囚 第1図 L511. /i  (ftVJ/cm2)Iθ   
 〃θ    lθ070θ津 −&   (nyn) A差水の光tンT0説明1:イ共する4i]第4図
FIG. 1 is a cross-sectional view showing an embodiment of the optical sensor of the present invention, FIG. 2 is a characteristic curve diagram showing the photoelectric conversion characteristics of the optical sensor of the invention with respect to light wavelength, and FIG. 3 is a diagram of the optical sensor of the invention. A characteristic curve diagram showing photoelectric conversion characteristics with respect to light intensity at a constant wavelength, FIG. 4 is a diagram for explaining a conventional optical sensor. 11... Insulating base (glass substrate) 13... First electrode (ITO transparent electrode) 15... Organic semiconductor layer (chloroindium naphthalocyanine) 17... Second electrode (aluminum back electrode). Patent applicant: Oki Electric Industry Co., Ltd. 17: 1 digit (γ) of the second and 5 near A beak 9 movements 1 &) This whole June's light 〉pu's prisoner Figure 1 L511. /i (ftVJ/cm2) Iθ
〃θ lθ070θtsu -& (nyn) A difference water light tton T0 Explanation 1: I share 4i] Figure 4

Claims (1)

【特許請求の範囲】[Claims] (1)光電変換層として有機半導体層を用いた光センサ
において、 該有機半導体層を下記構造式( I )で表わされるクロ
ロインジウムナフタロシアニンとしたことを特徴とする
光センサ。 ▲数式、化学式、表等があります▼( I )
(1) An optical sensor using an organic semiconductor layer as a photoelectric conversion layer, characterized in that the organic semiconductor layer is chloroindium naphthalocyanine represented by the following structural formula (I). ▲There are mathematical formulas, chemical formulas, tables, etc.▼(I)
JP60186897A 1985-08-26 1985-08-26 Photosensor Granted JPS6247169A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
JP60186897A JPS6247169A (en) 1985-08-26 1985-08-26 Photosensor

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
JP60186897A JPS6247169A (en) 1985-08-26 1985-08-26 Photosensor

Publications (2)

Publication Number Publication Date
JPS6247169A true JPS6247169A (en) 1987-02-28
JPH0587033B2 JPH0587033B2 (en) 1993-12-15

Family

ID=16196598

Family Applications (1)

Application Number Title Priority Date Filing Date
JP60186897A Granted JPS6247169A (en) 1985-08-26 1985-08-26 Photosensor

Country Status (1)

Country Link
JP (1) JPS6247169A (en)

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6438753A (en) * 1987-04-22 1989-02-09 Hitachi Chemical Co Ltd Electrophotographic sensitive body
JP2004335610A (en) * 2003-05-02 2004-11-25 National Institute Of Advanced Industrial & Technology Organic semiconductor devices
JP2008091694A (en) * 2006-10-03 2008-04-17 Seiko Electric Co Ltd Organic semiconductor photodetector
JP2010003902A (en) * 2008-06-20 2010-01-07 Fujifilm Corp Photoelectric converting material, photoelectric converting element, and solid-state image sensor
WO2016027675A1 (en) * 2014-08-20 2016-02-25 東レ株式会社 Photoelectric conversion element, and image sensor, solar cell, single color detection sensor and flexible sensor each of which uses said photoelectric conversion element

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6438753A (en) * 1987-04-22 1989-02-09 Hitachi Chemical Co Ltd Electrophotographic sensitive body
JP2004335610A (en) * 2003-05-02 2004-11-25 National Institute Of Advanced Industrial & Technology Organic semiconductor devices
JP2008091694A (en) * 2006-10-03 2008-04-17 Seiko Electric Co Ltd Organic semiconductor photodetector
JP2010003902A (en) * 2008-06-20 2010-01-07 Fujifilm Corp Photoelectric converting material, photoelectric converting element, and solid-state image sensor
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