JP2016532301A - 溶液から作製された無機半導体から空気中で安定な赤外線光検出器 - Google Patents
溶液から作製された無機半導体から空気中で安定な赤外線光検出器 Download PDFInfo
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- JP2016532301A JP2016532301A JP2016537915A JP2016537915A JP2016532301A JP 2016532301 A JP2016532301 A JP 2016532301A JP 2016537915 A JP2016537915 A JP 2016537915A JP 2016537915 A JP2016537915 A JP 2016537915A JP 2016532301 A JP2016532301 A JP 2016532301A
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- H01L31/08—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof in which radiation controls flow of current through the device, e.g. photoresistors
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- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0352—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions
- H01L31/035209—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures
- H01L31/035218—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their shape or by the shapes, relative sizes or disposition of the semiconductor regions comprising a quantum structures the quantum structure being quantum dots
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Abstract
Description
この出願は、2013年8月29日に出願された米国仮出願No.61/871,579の35U.S.C.§119(e)に基づく優先権を主張し、図形、表または図面を含むその全体は、ここに参照することで、この出願に組み込まれる。
を使用して表現することができる、光検出器の検出感度に関連する性能指数を参照することができる、ここで、Rは応答速度であり、Aは装置面積であり、Bは帯域幅であり、Idは暗電流密度であり、qは素電荷(1.6×10−19C)である。ここに使用されているように、空気安定性光検出器は、空気に対する露出により、ある一定の時間間隔に亘って、約50%以下、約20%以下、約10%以下、約5%以下、または、約1%以下の相対標準偏差を有する測定した性能測定基準を有する光検出器を参照することができる。ある実施例において、空気安定性光検出器は、約1%から約5%の範囲内、約1%から約10%の範囲内、約1%から約20%の範囲内、約1%から約50%の範囲内、約5%から約20%の範囲内、約5%から約50%の範囲内、約10%から約20%の範囲内、または、約10%から約50%の範囲内の相対標準偏差を有する測定した性能測定基準を有する。ある実施例において、時間間隔は、少なくとも約1日、少なくとも約10日、少なくとも約30日、少なくとも約60日、少なくとも約90日、少なくとも約120日、少なくとも約240日、少なくとも約1年、少なくとも約5年、または、少なくとも約10年である。時間間隔は、約1日から約30日の範囲内、約1日から約60日の範囲内、約1日から約90日の範囲内、約1日から約120日の範囲内、約1日から約240日の範囲内、約1日から約1年の範囲内、約1日から約5年の範囲内、約1日から約10年の範囲内、約30日から約60日の範囲内、約30日から約90日の範囲内、約30日から約120日の範囲内、約30日から約1年の範囲内、約60日から約120日の範囲内、約60日から約1年の範囲内、約60日から約5年の範囲内、約60日から約10年の範囲内、約90日から約120日の範囲内、約90日から約1年の範囲内、約90日から約5年の範囲内、約90日から約10年の範囲内、約120日から約1年の範囲内、約120日から約5年の範内、約120日から約10年の範囲内、約365日から約5年の範囲内、約365日から約10年の範囲内、または、約5年から約10年の範囲内とすることができる。あるケースにおいて、光検出器は、外部密封コーティング(すなわち、第1および第2の金属酸化物層以外)無しで空気安定性を有する。外部密封コーティング無しで空気安定性を有する特性は、光検出器の製造および貯蔵を有利に促進することができ、コストを削減することができる。
エタノール中ニッケルアセテートの0.1M溶液がエタノールアミンと1:1モル比で混合されたNiO前駆体溶液が、準備される。NiO前駆体溶液は、陽極上にスピンコーティングされ、空気中で1時間加熱される。加熱温度は、275℃から500℃あるいはそれ以上とすることができ、NiOの連続した膜を形成する。
オクタデカン中のヘキサメチルジシラシアン((TMS)2S)の1M溶液が、110℃および150℃の温度で、オクタデカンおよびオレイン酸中でしっかり撹拌された酸化鉛の0.004M溶液中に注入される。3−5分後、反応は冷却されたイソプロパノールの添加によって急冷される。急冷後、コロイド状のPbSが沈殿し、アセトンなどの非溶剤での遠心分離で3回洗浄される。PbSナノ粒子は、トルエン中に分散され、その後乾燥させる。量子ドットの懸濁液は、望ましい膜層厚を達成するために選択された濃度で装置の製造のために準備される。異なる吸収スペクトルを有する異なる大きさの量子ドットは、注入と冷却との間の反応温度および反応時間を制御することによって準備される。1000nmと1500nmとの間の第1の励起吸収ピークを有するPbSナノ粒子は、簡単に製造される。約6nmの直径の疑似球形の量子ドットは、可視域を介して延びる吸収尾部で準備される。これらの量子ドットは、概ね、以下のように特徴付けられる広帯域マルチスペクトル光検出器に適している。図3は、400nmから1300nmを介しての吸収を示す、6nm直径の量子ドットの応答速度を示す。直径が約4nmから約10nmの範囲の量子ドットは、この処理によって簡単に合成される。
ジメチルサルフォキシド(DMSO)中水酸化テトラメチルアンモニウム五水和物(TMAH)の10M溶液は、しっかり1時間撹拌されたエタノール中酢酸亜鉛ジハイドレードの10M溶液中に添加される。約6nmの直径を有するコロイド状のZnOナノ粒子が形成される。図5に示される、ZnOナノ粒子は、繰り返して、分散され、洗浄され、遠心分離される。コロイド状のZnOナノ粒子は、エタノール中で分散され、光活性層上に直接スピンコーティングされ、ZnO層を乾燥させるために、80℃で10分熱される。ZnOナノ粒子は、同様の大きさの多孔性PbS膜と密接に接触する。
6nmPbS量子ドット堆積の種々の数から形成された光活性層を備える光検出器に対し、逆バイアスでのダイオードの暗電流は、図6に示すように、1ナノアンペアのオーダーである。これは、NiOのp型の性質およびZnOのn型の性質を反映する、適切な電流整流作用を有する好ましい光検出器のレベルを示している。スペクトル光応答性は、図3に示すように、光検出器が、電磁スペクトルの近赤外部分から可視部分を介して延びる(例えば、約400nmから約1300nm)、広い吸収域を有することを示す。
を使用してノイズ等価電力(NEP)を計算するために使用される、ここでRはスペクトル応答速度である。比検出能D*は、次に、式:
を使用して計算される、ここでAは装置領域およびBは帯域幅である。
Claims (25)
- 光検出器であって:
半導体無機ナノ粒子を備える光活性層;
第1の金属酸化物を備えるホール輸送層;および
第2の金属酸化物を備える電子輸送層;を備え、
ナノ粒子はスペクトルの少なくとも赤外線領域において電磁放射に対し反応し、光活性層はホール輸送層と電子輸送層との間に位置し、光検出器は外側の封入被覆がなくても空気中で安定であることを特徴とする光検出器。 - 光検出器は、少なくとも約120日の期間に亘って、約5%未満の相対標準偏差を有する外部量子効率を有し、光検出器はその期間中空気に曝されることを特徴とする請求項1に記載の光検出器。
- ホール輸送層がホール輸送電子阻止層であることを特徴とする請求項1に記載の光検出器。
- 電子輸送層が電子輸送ホール阻止層であることを特徴とする請求項1に記載の光検出器。
- 第1の金属酸化物がNiOであることを特徴とする請求項1に記載の光検出器。
- 第2の金属酸化物がZnOまたはTiO2であることを特徴とする請求項1に記載の光検出器。
- 第2の金属酸化物がZnOであることを特徴とする請求項1に記載の光検出器。
- 半導体無機ナノ粒子が、鉛カルコゲニド、鉛カルコゲニドの合金、水銀カルコゲニド、水銀カルコゲニドの合金、インジウムおよび/またはガリウムに基づくIII−V族半導体、シリコンまたはそれらの組み合わせを備えることを特徴とする請求項1に記載の光検出器。
- 半導体無機ナノ粒子がPbSまたはPbSeを備えることを特徴とする請求項1に記載の光検出器。
- ナノ粒子が、電磁スペクトルの可視および赤外線領域において、電磁放射に対し反応することを特徴とする請求項1に記載の光検出器。
- さらにホール抽出層を備えることを特徴とする請求項1に記載の光検出器。
- ホール抽出層が、酸化モリブデン(MoO3)、酸化タングステン(WO3)、および/または、酸化バナジウム(V2O5)を備えることを特徴とする請求項9に記載の光検出器。
- さらに光検出器の光入射面上に光ファイバーを備えることを特徴とする請求項1に記載の光検出器。
- 光ファイバーが、電磁スペクトルの紫外線領域において、電磁放射の少なくとも一部を取り除くことを特徴とする請求項1に記載の光検出器。
- 請求項1に記載の光検出器を準備する方法であって:
電極を備える基板を提供する工程;
第1の金属酸化物前駆体の第1の溶液または複数の金属酸化物粒子の第1の懸濁液を、電極上に堆積する工程;
第1の溶液または第1の懸濁液から溶媒を取り除き、第1の金属酸化物を備える第1の層を形成する工程;
半導体無機ナノ粒子のコロイド懸濁液を第1の層上に堆積する工程;
半導体無機量子ドットのコロイド懸濁液から溶媒を取り除き、半導体無機量子ドットを備える光活性層を形成する工程;
第2の金属酸化物前駆体の第2の溶液または複数の金属酸化物粒子の第2の懸濁液を、光活性層上に堆積する工程;および
第2の溶液または第2の懸濁液から溶媒を取り除き、第2の金属酸化物を備える第2の層を形成する工程;
を備えることを特徴とする光検出器を準備する方法。 - 電極が陽極であり、第1の金属酸化物を備える第1の層がホール輸送電子阻止層であり、第2の金属酸化物を備える第2の層が電子輸送ホール阻止層であることを特徴とする請求項15に記載の方法。
- 電極が陰極であり、第1の金属酸化物を備える第1の層が電子輸送ホール阻止層であり、第2の金属酸化物を備える第2の層がホール輸送電子阻止層であることを特徴とする請求項15に記載の方法。
- ホール輸送電子阻止層がNiOを備えることを特徴とする請求項16または17に記載の方法。
- 電子輸送ホール阻止層がZnOおよび/またはTiO2を備えることを特徴とする請求項16または17に記載の方法。
- さらに、第1の金属酸化物を備える第1の層、第2の金属酸化物を備える第2の層、および/または、光活性層を、化学的にまたは熱的に変える工程を備えることを特徴とする請求項15に記載の方法。
- 第1の金属酸化物を備える第1の層、第2の金属酸化物を備える第2の層、および/または、光活性層を化学的に変える工程が、リガンド交換を備えることを特徴とする請求項20に記載の方法。
- 方法が、さらに、光検出器を密封する工程を含まないことを特徴とする請求項15に記載の方法。
- さらに、光検出器を一時期空気に曝す工程であって、光検出器の性能が一時期の間安定している工程を備えることを特徴とする請求項15に記載の方法。
- 一時期が少なくとも約120日であることを特徴とする請求項23に記載の方法。
- 光検出器が、一時期の間約5%未満の相対標準偏差を有する外部量子効率を有することを特徴とする請求項23に記載の方法。
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PCT/US2014/053546 WO2015031835A1 (en) | 2013-08-29 | 2014-08-29 | Air stable infrared photodetectors from solution-processed inorganic semiconductors |
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KR102429174B1 (ko) | 2017-07-12 | 2022-08-03 | 현대자동차주식회사 | 양자점 태양 전지용 광활성층의 제조 방법 및 양자점 태양 전지의 제조 방법 |
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JP7391600B2 (ja) | 2019-10-11 | 2023-12-05 | キヤノン株式会社 | 光電変換素子 |
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CN105493295B (zh) | 2019-03-29 |
WO2015031835A1 (en) | 2015-03-05 |
EP3039724A1 (en) | 2016-07-06 |
KR20160078954A (ko) | 2016-07-05 |
EP3039724A4 (en) | 2017-06-21 |
CN105493295A (zh) | 2016-04-13 |
US9985153B2 (en) | 2018-05-29 |
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US20160211392A1 (en) | 2016-07-21 |
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