JP6270498B2 - Radiation detection element and method for manufacturing radiation detection element - Google Patents
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- 230000005855 radiation Effects 0.000 title claims description 74
- 238000001514 detection method Methods 0.000 title claims description 47
- 238000000034 method Methods 0.000 title claims description 30
- 238000004519 manufacturing process Methods 0.000 title claims description 12
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- 238000005530 etching Methods 0.000 claims description 9
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- 238000001228 spectrum Methods 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 9
- 239000013078 crystal Substances 0.000 description 9
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- QWUZMTJBRUASOW-UHFFFAOYSA-N cadmium tellanylidenezinc Chemical compound [Zn].[Cd].[Te] QWUZMTJBRUASOW-UHFFFAOYSA-N 0.000 description 7
- 239000000203 mixture Substances 0.000 description 7
- 238000004381 surface treatment Methods 0.000 description 7
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- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 3
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- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 2
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 229910052782 aluminium Inorganic materials 0.000 description 2
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 2
- 230000015572 biosynthetic process Effects 0.000 description 2
- 238000001312 dry etching Methods 0.000 description 2
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 2
- 229910052737 gold Inorganic materials 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- APFVFJFRJDLVQX-UHFFFAOYSA-N indium atom Chemical compound [In] APFVFJFRJDLVQX-UHFFFAOYSA-N 0.000 description 2
- 239000011259 mixed solution Substances 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000007517 polishing process Methods 0.000 description 2
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- XSOKHXFFCGXDJZ-UHFFFAOYSA-N telluride(2-) Chemical compound [Te-2] XSOKHXFFCGXDJZ-UHFFFAOYSA-N 0.000 description 2
- 238000007738 vacuum evaporation Methods 0.000 description 2
- 238000007740 vapor deposition Methods 0.000 description 2
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 2
- WKBOTKDWSSQWDR-UHFFFAOYSA-N Bromine atom Chemical compound [Br] WKBOTKDWSSQWDR-UHFFFAOYSA-N 0.000 description 1
- KZBUYRJDOAKODT-UHFFFAOYSA-N Chlorine Chemical compound ClCl KZBUYRJDOAKODT-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- KRHYYFGTRYWZRS-UHFFFAOYSA-N Fluorane Chemical compound F KRHYYFGTRYWZRS-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- MODGUXHMLLXODK-UHFFFAOYSA-N [Br].CO Chemical class [Br].CO MODGUXHMLLXODK-UHFFFAOYSA-N 0.000 description 1
- SUMDBFHIHLAZCX-UHFFFAOYSA-J [Se](=O)([O-])[O-].[Cd+2].[Zn+2].[Se](=O)([O-])[O-] Chemical compound [Se](=O)([O-])[O-].[Cd+2].[Zn+2].[Se](=O)([O-])[O-] SUMDBFHIHLAZCX-UHFFFAOYSA-J 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 229910052786 argon Inorganic materials 0.000 description 1
- -1 brometa Chemical compound 0.000 description 1
- GDTBXPJZTBHREO-UHFFFAOYSA-N bromine Substances BrBr GDTBXPJZTBHREO-UHFFFAOYSA-N 0.000 description 1
- 229910052794 bromium Inorganic materials 0.000 description 1
- CEKJAYFBQARQNG-UHFFFAOYSA-N cadmium zinc Chemical compound [Zn].[Cd] CEKJAYFBQARQNG-UHFFFAOYSA-N 0.000 description 1
- KBJQPSPKRGXBTH-UHFFFAOYSA-L cadmium(2+);selenite Chemical compound [Cd+2].[O-][Se]([O-])=O KBJQPSPKRGXBTH-UHFFFAOYSA-L 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
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- 229910052732 germanium Inorganic materials 0.000 description 1
- GNPVGFCGXDBREM-UHFFFAOYSA-N germanium atom Chemical compound [Ge] GNPVGFCGXDBREM-UHFFFAOYSA-N 0.000 description 1
- 229910052736 halogen Inorganic materials 0.000 description 1
- 150000002367 halogens Chemical class 0.000 description 1
- 239000001307 helium Substances 0.000 description 1
- 229910052734 helium Inorganic materials 0.000 description 1
- SWQJXJOGLNCZEY-UHFFFAOYSA-N helium atom Chemical compound [He] SWQJXJOGLNCZEY-UHFFFAOYSA-N 0.000 description 1
- 150000004687 hexahydrates Chemical class 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
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- 229910052754 neon Inorganic materials 0.000 description 1
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Description
本発明は、化合物半導体結晶を基板とする放射線検出素子、およびこの放射線検出素子を製造する方法に関する。 The present invention relates to a radiation detection element using a compound semiconductor crystal as a substrate, and a method for manufacturing the radiation detection element.
従来、放射線検出素子の基板として用いるための、直接変換型化合物半導体の開発が進められてきている。その中でもII-VI族化合物半導体であるテルル化カドミウム（ＣｄＴｅ）、セレンテルル化カドミウム（ＣｄＳｅＴｅ）、テルル化亜鉛カドミウム（ＣｄＺｎＴｅ）、セレンテルル化亜鉛カドミウム（ＣｄＺｎＳｅＴｅ）は、近年有力な材料として注目されている。これらを基板とする放射線検出素子を備える放射線検出器は、シリコンやゲルマニウムを基板としたものに比べ、（１）原子番号が比較的大きいことから放射線の検出効率が高い、（２）バンドギャップが大きいので、熱ノイズ電流の影響が少なく冷却装置が不要であり、装置の小型化が可能、という利点がある。 Conventionally, development of a direct conversion type compound semiconductor for use as a substrate of a radiation detection element has been advanced. Among them, cadmium telluride (CdTe), cadmium selenite telluride (CdSeTe), zinc cadmium telluride (CdZnTe) and zinc cadmium selenite telluride (CdZnSeTe), which are II-VI group compound semiconductors, have been attracting attention as promising materials in recent years. . Radiation detectors equipped with radiation detection elements based on these substrates have (1) a relatively high atomic number because of the relatively large atomic number compared to silicon and germanium substrates, and (2) a band gap. Since it is large, there is an advantage that the influence of the thermal noise current is small, a cooling device is unnecessary, and the device can be downsized.
特に、近年では、検出特性を高めるため、基板の一方の主面に金（Ａｕ）や白金（Ｐｔ）等の仕事関数の大きな金属で、基板とオーミック接合する電極（以下第１電極）が形成され、他方の主面にインジウム（Ｉｎ）やアルミニウム（Ａｌ）等の仕事関数の小さな金属で、基板にショットキー接合する電極（以下第２電極）が形成されたショットキー型の放射線検出素子の開発が進められている（特許文献１、非特許文献１参照）。ショットキー型の放射線検出素子は、リーク電流を抑えることができることから、より高い電圧を印加することが可能となり、微弱な放射線の検出も可能となる。 In particular, in recent years, in order to improve detection characteristics, an electrode (hereinafter referred to as a first electrode) is formed on one main surface of the substrate with a metal having a large work function such as gold (Au) or platinum (Pt), which is in ohmic contact with the substrate. And a Schottky type radiation detecting element in which an electrode (hereinafter referred to as a second electrode) formed with a metal having a small work function, such as indium (In) or aluminum (Al), on the other main surface, is formed on the substrate. Development is in progress (see Patent Document 1 and Non-Patent Document 1). Since the Schottky type radiation detection element can suppress a leak current, it is possible to apply a higher voltage and detect weak radiation.
しかしながら、従来のショットキー型の放射線検出素子を用いた放射線検出器によって放射線計数スペクトルを得た場合、図４（ｂ）に示すように、低エネルギー側の裾が持ち上がる、といった現象が見られることがあった。この裾の持ち上がりは、素子のエネルギー分解能を劣化させる原因となっている。 However, when a radiation count spectrum is obtained by a radiation detector using a conventional Schottky type radiation detection element, a phenomenon that the bottom of the low energy side is lifted as shown in FIG. 4B is observed. was there. This lifting of the skirt causes the energy resolution of the element to deteriorate.
本発明は、上記課題に鑑みてなされたもので、基板の一方の主面に、基板とショットキー接合する第１電極が形成され、他方の主面に、基板とオーミック接合する第２電極が形成された放射線検出素子を備えた放射線検出器において、放射線計数スペクトルの低エネルギー側の裾が持ち上がらないようにすることを目的とする。 The present invention has been made in view of the above problems. A first electrode that is Schottky bonded to the substrate is formed on one main surface of the substrate, and a second electrode that is ohmic-bonded to the substrate is formed on the other main surface. An object of the present invention is to prevent a skirt on the low energy side of a radiation count spectrum from being lifted in a radiation detector including the formed radiation detection element.
発明者は、上記課題の解決のために鋭意研究を進めたところ、基板を形成するＣｄＴｅ等の化合物半導体と第２電極との接合部の状態が、放射線計数スペクトルの低エネルギー側の裾の持ち上がりと大きく関係していることを見出した。具体的には、接合部に含まれる酸素が放射線検出素子の検出特性を劣化させていることが分かった。すなわち、化合物半導体と第２電極との接合部に酸素が含まれると、その酸素がキャリアをトラップする準位を形成してしまうので、放射線を受けることにより生成されたキャリアがトラップされてしまう。このキャリアは、本来、放射線の検出信号となるものであり、そのキャリアがトラップされて取り出せなくなるということは、検出信号の劣化に繋がる。従って、基板と第２電極との接合部における酸素濃度を低くすることが必要である。
そこで、更に研究を進めた結果、第２電極を形成する前に行っている基板の表面処理方法を工夫することで、接合部の酸素濃度を下げることができるという知見を得て本発明に至った。
The inventor has intensively studied to solve the above problems, and as a result, the state of the joint between the compound semiconductor such as CdTe and the second electrode forming the substrate is raised on the lower energy side of the radiation counting spectrum. It was found that it is greatly related. Specifically, it was found that oxygen contained in the joint deteriorates the detection characteristics of the radiation detection element. That is, when oxygen is contained in the junction between the compound semiconductor and the second electrode, the oxygen forms a level for trapping carriers, so that carriers generated by receiving radiation are trapped. This carrier is essentially a radiation detection signal, and the fact that the carrier is trapped and cannot be taken out leads to deterioration of the detection signal. Therefore, it is necessary to reduce the oxygen concentration at the junction between the substrate and the second electrode.
Therefore, as a result of further research, the inventors have obtained the knowledge that the oxygen concentration at the junction can be lowered by devising the substrate surface treatment method performed before forming the second electrode. It was.
本発明は、基板と、前記基板の一方の主面に、前記基板とオーミック接合するように形成された第１電極と、前記基板の他方の主面に、前記基板とショットキー接合するように形成された第２電極と、を備える放射線検出素子であって、前記基板と前記第２電極との接合部のうち、前記第２電極を構成する元素の濃度が５０％となる箇所から前記他方の主面と直交する方向に±１５ｎｍの範囲における酸素濃度が１原子％以下となっていることを特徴とする。 The present invention provides a substrate, a first electrode formed on one main surface of the substrate so as to be in ohmic contact with the substrate, and a Schottky junction with the substrate on the other main surface of the substrate. A radiation detection element comprising: the second electrode formed; and the other of the junction part between the substrate and the second electrode from a position where the concentration of the element constituting the second electrode is 50%. The oxygen concentration in the range of ± 15 nm in the direction orthogonal to the main surface of the film is 1 atomic% or less.
従来は、基板と第２電極との接合部に存在する酸素がキャリアをトラップする準位を形成することで、検出信号が劣化していたが、本発明に係る放射線検出素子は、接合部における酸素濃度が低いので、生成されたキャリアがトラップされることなく検出信号となる。従って、本発明に係る放射線検出素子を用いれば、放射線計数スペクトルの低エネルギー側の裾が持ち上がらないようにすることができる。 Conventionally, the detection signal is deteriorated by forming a level at which oxygen present at the junction between the substrate and the second electrode traps carriers. However, the radiation detection element according to the present invention is provided at the junction. Since the oxygen concentration is low, the generated carrier becomes a detection signal without being trapped. Therefore, if the radiation detection element according to the present invention is used, it is possible to prevent the bottom of the low energy side of the radiation count spectrum from being lifted.
また、本発明は、基板と、前記基板の一方の主面に、前記基板とオーミック接合するように形成された第１電極と、前記基板の他方の主面に、前記基板とショットキー接合するように形成された第２電極と、を備える放射線検出素子の製造方法において、前記基板の他方の主面を、酸素を含まないエッチングガスを用いてドライエッチングし、その後、前記基板を非酸化性雰囲気に晒したまま、前記他方の主面に前記第２電極を形成することを特徴とする。
なお、「酸素を含まないエッチングガス」は、気体酸素が混合されていないガスと、酸素が成分として含まれていない分子からなるガスの両方を指す。
The present invention also includes a substrate, a first electrode formed on one main surface of the substrate so as to be in ohmic contact with the substrate, and a Schottky junction with the substrate on the other main surface of the substrate. In the manufacturing method of the radiation detecting element comprising the second electrode formed as described above, the other main surface of the substrate is dry-etched using an etching gas not containing oxygen, and then the substrate is made non-oxidizing The second electrode is formed on the other main surface while being exposed to the atmosphere.
The “etching gas not containing oxygen” refers to both a gas not containing gaseous oxygen and a gas composed of molecules not containing oxygen as a component.
従来は、エッチャントに含まれる酸素が、エッチングの際に基板表面に付着し、第２電極の形成後も、基板と第２電極との接合部に残留してしまっていたが、本発明に係る放射線検出素子の製造方法によれば、エッチングの際に基板に酸素が付着することがなくなるので、基板と第２電極との接合部における酸素濃度を下げることができる。 Conventionally, oxygen contained in the etchant adheres to the surface of the substrate during etching and remains at the junction between the substrate and the second electrode even after the formation of the second electrode. According to the method for manufacturing a radiation detection element, oxygen does not adhere to the substrate during etching, so that the oxygen concentration at the junction between the substrate and the second electrode can be lowered.
本発明によれば、基板の一方の主面に、基板とショットキー接合する第１電極が形成され、他方の主面に、基板とオーミック接合する第２電極が形成された放射線検出素子を備えた放射線検出器において、放射線計数スペクトルの低エネルギー側の裾が持ち上がらないようにすることができる。 According to the present invention, the radiation detection element having the first electrode that is Schottky-bonded to the substrate on one main surface of the substrate and the second electrode that is ohmic-bonded to the substrate is formed on the other main surface. In the radiation detector, it is possible to prevent the bottom of the low energy side of the radiation counting spectrum from being lifted.
以下、図面を参照して、本発明の実施形態について詳細に説明する。 Hereinafter, embodiments of the present invention will be described in detail with reference to the drawings.
〔放射線検出素子の構成〕
まず、本実施形態の放射線検出素子の構成について説明する。図１は本実施形態の放射線検出素子１０の一例を示す斜視図、図２（ａ）は図１のII−II断面図、図２（ｂ）は（ａ）の矢印に沿う方向の組成の変化を示すグラフ、図２（ｃ）は（ｂ）の一部を縦方向に拡大したグラフである。
放射線検出素子１０は、図１に示すように、基板１、基板１の一方の主面（以下Ａ面１ａ）に形成されたオーミック電極２、基板１の他方の主面（以下Ｂ面１ｂ）に形成されたショットキー電極３、で構成されている。
[Configuration of radiation detection element]
First, the structure of the radiation detection element of this embodiment is demonstrated. 1 is a perspective view showing an example of the radiation detection element 10 of the present embodiment, FIG. 2A is a cross-sectional view taken along the line II-II in FIG. 1, and FIG. 2B is a composition in the direction along the arrow in FIG. FIG. 2C is a graph in which a part of FIG. 2B is enlarged in the vertical direction.
As shown in FIG. 1, the radiation detection element 10 includes a substrate 1, an ohmic electrode 2 formed on one main surface (hereinafter referred to as A surface 1a) of the substrate 1, and the other main surface (hereinafter referred to as B surface 1b) of the substrate 1. The Schottky electrode 3 is formed.
基板１は、II−VI族化合物半導体単結晶であるテルル化カドミウム（ＣｄＴｅ）単結晶、セレンテルル化カドミウム（ＣｄＳｅＴｅ）単結晶、テルル化亜鉛カドミウム（ＣｄＺｎＴｅ）単結晶、またはセレンテルル化亜鉛カドミウム（ＣｄＺｎＳｅＴｅ）単結晶、で、主面が矩形（図は正方形）の薄い板状に形成されている。また、基板１の主面は、所定の結晶面（例えば（１１１）面）となっている。
オーミック電極２は、金（Ａｕ）、白金（Ｐｔ）等の仕事関数の大きな金属の薄膜で基板１１のＡ面１ａ全体を覆うように形成されている。すなわち、オーミック電極２は、基板１とオーミック接合している。
ショットキー電極３は、例えばインジウム（Ｉｎ）やアルミニウム（Ａｌ）等の仕事関数の小さな金属の薄膜で形成されている。すなわち、ショットキー電極３は、基板１とショットキー接合している。なお、ショットキー電極３は、Ｂ面１ｂ全体を覆うように形成したものとしてもよいし、図１に示したように、複数の微小なピクセル状のものをマトリクス（行列）状に配列したものとしてもよい。
The substrate 1 includes a cadmium telluride (CdTe) single crystal, a cadmium telluride (CdSeTe) single crystal, a cadmium zinc telluride (CdZnTe) single crystal, or a cadmium zinc telluride (CdZnSeTe). It is a single crystal and is formed in a thin plate shape whose main surface is rectangular (square in the figure). The main surface of the substrate 1 is a predetermined crystal plane (for example, (111) plane).
The ohmic electrode 2 is formed so as to cover the entire A surface 1a of the substrate 11 with a thin metal film having a large work function such as gold (Au) or platinum (Pt). That is, the ohmic electrode 2 is in ohmic contact with the substrate 1.
The Schottky electrode 3 is formed of a thin metal film having a small work function such as indium (In) or aluminum (Al). That is, the Schottky electrode 3 is in Schottky junction with the substrate 1. Note that the Schottky electrode 3 may be formed so as to cover the entire B surface 1b, or as shown in FIG. 1, a plurality of minute pixel-like elements arranged in a matrix. It is good.
また、図２（ａ）に示すように、基板１の内部（Ｉｎが含まれない領域）の所定箇所を起点Ｏとして、矢印が示す方向（Ｂ面１ｂと直交し、ショットキー電極３に近づく方向）に向かうに従って、放射線検出素子１０の組成がどのように変化していくかを、エネルギー分散型蛍光Ｘ線分析法を用いて調べると、図２（ｂ）に示すようなグラフが得られる。そして、Ｉｎ濃度が５０％となる箇所を通り、Ｂ面１ｂと並行な面を基板１とショットキー電極３の界面Ｓと定義し、起点Ｏから界面Ｓまでの距離を得られたグラフから求め（図２の場合は起点から約２２ｎｍ）、界面Ｓから界面Ｓと直交する方向に向かって±１５ｎｍの範囲（起点から約６〜３６ｎｍの部位、以下界面近傍領域Ｔ）における酸素濃度を調べると、図２（ｃ）に示すように、１ａｔ％未満となっている。 Further, as shown in FIG. 2A, a predetermined location inside the substrate 1 (region not including In) is a starting point O, and the direction indicated by the arrow (perpendicular to the B surface 1b and approaches the Schottky electrode 3). If the energy dispersive X-ray fluorescence analysis method is used to examine how the composition of the radiation detection element 10 changes in the direction (direction), a graph as shown in FIG. 2B is obtained. . Then, a surface passing through a portion where the In concentration is 50% and parallel to the B surface 1b is defined as the interface S between the substrate 1 and the Schottky electrode 3, and the distance from the starting point O to the interface S is obtained from the obtained graph. (In the case of FIG. 2, about 22 nm from the starting point), when examining the oxygen concentration in the range of ± 15 nm from the interface S in the direction orthogonal to the interface S (part of about 6 to 36 nm from the starting point, hereinafter the interface vicinity region T) As shown in FIG. 2C, it is less than 1 at%.
〔放射線検出素子の製造方法〕
次に、上記放射線検出素子の製造方法について説明する。
放射線検出素子１０は、基板製造工程、電極形成工程、ダイシング工程を経て製造される。
はじめに行われる基板製造工程は、切断工程、研磨工程からなる。
切断工程では、ＣｄＴｅ等の単結晶インゴットを所定の結晶面に沿って切断することにより薄い円盤状のウェハ（基板１）を切り出す。
切断工程の後は、研磨工程に移る。研磨工程では、切り出したウェハの切断面をアルミナ粉末等の研磨剤を用いて物理的に鏡面研磨する。この研磨工程は、ウェハ毎に複数回繰り返してもよい。
[Method of manufacturing radiation detection element]
Next, the manufacturing method of the said radiation detection element is demonstrated.
The radiation detection element 10 is manufactured through a substrate manufacturing process, an electrode forming process, and a dicing process.
The substrate manufacturing process performed first includes a cutting process and a polishing process.
In the cutting step, a thin disk-shaped wafer (substrate 1) is cut out by cutting a single crystal ingot such as CdTe along a predetermined crystal plane.
After the cutting process, the process proceeds to the polishing process. In the polishing step, the cut surface of the cut wafer is physically mirror-polished using an abrasive such as alumina powder. This polishing step may be repeated multiple times for each wafer.
基板製造工程の後は電極形成工程に移る。電極形成工程は、表面処理工程、ショットキー電極形成工程、オーミック電極形成工程からなる。
表面処理工程では、まず、基板製造工程で製造されたウェハを製造装置にセットし、ウェハのＢ面１ｂを、ドライエッチング（プラズマエッチングや反応性イオンエッチング）する。具体的には、酸素を含まないエッチングガス（例えば、アルゴン（Ａｒ）、ヘリウム（Ｈｅ）、ネオン（Ｎｅ）、窒素（Ｎ２）等他の不活性ガス、フッ素（Ｆ２）、塩素（Ｃｌ２）、フッ化水素（ＨＦ）、塩化水素（ＨＣｌ）等のハロゲン系ガス、またはハイドライド系のガス）を、イオンまたはラジカルにしたものを、基板に衝突させることにより、Ｂ面１ｂに付着した異物や加工変質層を除去する。従来は、ブロメタ等、酸素を含むエッチャントでエッチングしていたため、この工程でエッチャントの酸素がウェハ表面に付着する可能性があったが、本実施形態のようにすることで、ウェハ表面に酸素が付着することがない。
After the substrate manufacturing process, the process proceeds to an electrode forming process. The electrode forming process includes a surface treatment process, a Schottky electrode forming process, and an ohmic electrode forming process.
In the surface treatment process, first, the wafer manufactured in the substrate manufacturing process is set in a manufacturing apparatus, and the B surface 1b of the wafer is dry-etched (plasma etching or reactive ion etching). Specifically, an etching gas not containing oxygen (for example, other inert gases such as argon (Ar), helium (He), neon (Ne), nitrogen (N2), fluorine (F2), chlorine (Cl2), Foreign matter or processing adhering to the B surface 1b by causing ions or radicals of halogen-based gas such as hydrogen fluoride (HF) or hydrogen chloride (HCl) or hydride-based gas to collide with the substrate. Remove the altered layer. Conventionally, since etching was performed with an etchant containing oxygen such as brometa, there was a possibility that the oxygen of the etchant might adhere to the wafer surface in this step. However, by using this embodiment, oxygen is added to the wafer surface. There is no adhesion.
表面処理工程の後はショットキー電極形成工程に移る。ショットキー電極形成工程は、形成しようとするショットキー電極の数や大きさによって処理が異なる。ピクセル状のショットキー電極３を複数形成する場合は、ウェハのＢ面１ｂ全体にフォトレジストを塗布し、ピクセル電極パターンが描かれたフォトマスクを用いてフォトレジストを露光する。そして、現像することにより感光したフォトレジストを除去する。そして、メタノールを用いてウェハからブロメタ液を除去し、純水を用いてウェハからメタノールを除去する。その後、ウェハのＢ面１ｂのフォトレジストの除去された（Ｂ面１ｂが露出した）箇所に、蒸着やスパッタリングなどの物理気相堆積（ＰＶＤ）法、或いは化学気相堆積（ＣＶＤ）法を用いてＩｎ層を形成する。このＩｎ層が所定の膜厚まで成長したものがショットキー電極３となる。一方、Ｂ面１ｂ全体を覆うようなショットキー電極３を形成する場合は、上述したフォトレジスト膜形成する工程を経ずに、表面処理を終えたウェハのＢ面１ｂ全体にＰＶＤ法またはＣＶＤ法でＩｎ層を形成していくことによりショットキー電極３を形成する。 After the surface treatment process, the process proceeds to a Schottky electrode formation process. The processing of the Schottky electrode forming process varies depending on the number and size of Schottky electrodes to be formed. When a plurality of pixel-shaped Schottky electrodes 3 are formed, a photoresist is applied to the entire B surface 1b of the wafer, and the photoresist is exposed using a photomask on which a pixel electrode pattern is drawn. Then, the exposed photoresist is removed by development. Then, the brometa solution is removed from the wafer using methanol, and the methanol is removed from the wafer using pure water. Thereafter, a physical vapor deposition (PVD) method such as vapor deposition or sputtering, or a chemical vapor deposition (CVD) method is used on the B surface 1b of the wafer where the photoresist is removed (the B surface 1b is exposed). Then, an In layer is formed. The In layer grown to a predetermined thickness is the Schottky electrode 3. On the other hand, when the Schottky electrode 3 is formed so as to cover the entire B surface 1b, the PVD method or the CVD method is applied to the entire B surface 1b of the wafer after the surface treatment without passing through the above-described photoresist film forming step. The Schottky electrode 3 is formed by forming the In layer in step (b).
ショットキー電極形成工程の後はオーミック電極形成工程に移る。オーミック電極形成工程では、ウェハを塩化白金酸（IV）六水和物水溶液に塩酸を混合しためっき液に浸漬し、ウェハのＡ面１ａ全体にＰｔを析出させることでＰｔ層を形成する。このＰｔ層が所定の膜厚まで成長したものがオーミック電極２となる。オーミック電極２が形成された後は、不要になったフォトレジストを除去し、純水を用いてウェハを洗浄する。そして、ウェハに窒素ガスを噴きつけることによりウェハを乾燥させて電極形成工程を終了する。 After the Schottky electrode forming process, the process proceeds to the ohmic electrode forming process. In the ohmic electrode forming step, the wafer is immersed in a plating solution in which hydrochloric acid is mixed with a chloroplatinic acid (IV) hexahydrate solution, and Pt is deposited on the entire A surface 1a of the wafer to form a Pt layer. The Pt layer grown to a predetermined film thickness is the ohmic electrode 2. After the ohmic electrode 2 is formed, the unnecessary photoresist is removed, and the wafer is washed with pure water. Then, the wafer is dried by spraying nitrogen gas onto the wafer, and the electrode forming step is completed.
電極形成工程の後はダイシング工程に移る。ダイシング工程では、Ａ面１ａにオーミック電極２、Ｂ面１ｂにショットキー電極３が形成されたウェハを切断して複数の基板１に分割するとともに、個々の放射線検出素子１０をウェハから切り出す。
以上の各工程を経ることにより、界面近傍領域Ｔにおける酸素濃度が低い本実施形態の放射線検出素子１０が製造される。
After the electrode forming process, the process proceeds to a dicing process. In the dicing process, the wafer having the ohmic electrode 2 formed on the A surface 1a and the Schottky electrode 3 formed on the B surface 1b is cut and divided into a plurality of substrates 1, and the individual radiation detection elements 10 are cut out from the wafer.
Through the above steps, the radiation detection element 10 of the present embodiment having a low oxygen concentration in the interface vicinity region T is manufactured.
〔放射線検出素子の特性〕
次に、上記放射線検出素子の特性について説明する。
発明者は、本実施形態の放射線検出素子のエネルギー分解能と、従来の放射線検出素子のエネルギー分解能の差を確認するために、下記３種類の実験（実施例１，２および比較例）を行った。
[Characteristics of radiation detector]
Next, the characteristics of the radiation detection element will be described.
The inventor conducted the following three types of experiments (Examples 1, 2 and Comparative Example) in order to confirm the difference between the energy resolution of the radiation detection element of this embodiment and the energy resolution of the conventional radiation detection element. .
（実施例１）
まず、ＣｄＺｎＴｅ基板の（１１１）Ｂ面にＡｒガスでプラズマエッチングを行って表面の加工変質層を除去した。この後、基板を真空蒸着炉内にセットし、Ｂ面全体にＩｎを厚さ３００ｎｍとなるまで蒸着してショットキー電極を形成した。そして、炉内を真空引きし、基板を２００℃でアニールした。その後、基板の（１１１）Ａ面全体に無電解めっきでＰｔを厚さ５０ｎｍとなるまで析出させオーミック電極を形成した。
このようにして作成した実施例サンプルの、基板とショットキー電極との接合部におけるＢ面と直交する方向の組成の変化をエネルギー分散型蛍光Ｘ線分析法で調べたところ、図２（ｂ），（ｃ）に示したグラフが得られた。このグラフからは、界面近傍領域Ｔ（起点から約６〜３６ｎｍ）における酸素濃度は１ａｔ％未満であることが見て取れる。
そして、この実施例サンプルを用いて放射線検出器を構成し、この放射線検出器にＣｏ５７を放射線源とする放射線を照射したところ、図４（ａ）に示すＭＣＡスペクトルが得られた。このスペクトルからは、Ｃｏ５７が固有にもつ１２２．２ｋｅＶのピークが鋭く現れ、低エネルギー側のスペクトルの裾野が下がっていることも見て取れる。なお、このピークの印加電圧５００Ｖにおける半値幅は４．３％と低かった。
Example 1
First, the (111) B surface of the CdZnTe substrate was subjected to plasma etching with Ar gas to remove the work-affected layer on the surface. Thereafter, the substrate was set in a vacuum vapor deposition furnace, and In was vapor-deposited on the entire B surface to a thickness of 300 nm to form a Schottky electrode. Then, the inside of the furnace was evacuated and the substrate was annealed at 200 ° C. Thereafter, Pt was deposited on the entire (111) A surface of the substrate by electroless plating to a thickness of 50 nm to form an ohmic electrode.
When the change in the composition in the direction perpendicular to the B-plane at the junction between the substrate and the Schottky electrode in the sample of the example prepared as described above was examined by energy dispersive X-ray fluorescence analysis, FIG. The graph shown in (c) was obtained. From this graph, it can be seen that the oxygen concentration in the interface vicinity region T (about 6 to 36 nm from the starting point) is less than 1 at%.
And when the radiation detector was comprised using this Example sample and this radiation detector was irradiated with the radiation which used Co57 as a radiation source, the MCA spectrum shown to Fig.4 (a) was obtained. From this spectrum, it can be seen that the peak of 122.2 keV inherent to Co57 appears sharply, and the base of the spectrum on the low energy side is lowered. The full width at half maximum at an applied voltage of 500 V at this peak was as low as 4.3%.
（実施例２）
次に、実施例１と同じＣｄＺｎＴｅ基板の（１１１）Ｂ面にＡｒガスでプラズマエッチングを行って表面の加工変質層を除去した。この後、Ｂ面にピクセル電極パターン形状の開口を有するマスクを形成し、基板を真空蒸着炉内にセットして、マスクの開口から露出したＢ面にＩｎを厚さ３００ｎｍとなるまで蒸着してピクセル状のショットキー電極を複数形成した。そして、炉内を真空引きし、基板を２００℃でアニールした。その後、基板の（１１１）Ａ面全体に無電解めっきでＰｔを厚さ５０ｎｍとなるまで析出させオーミック電極を形成した。
このようにして作成した実施例サンプルの、基板とショットキー電極との接合部におけるＢ面と直交する方向の組成の変化をエネルギー分散型蛍光Ｘ線分析法で調べたところ、実施例１と同様の、界面近傍領域Ｔにおける酸素濃度が１ａｔ％未満となっているグラフが得られた。
そして、この実施例サンプルを用いて放射線検出器を構成し、この放射線検出器にＣｏ５７を放射線源とする放射線を照射したところ、実施例１と同様の、１２２．２ｋｅＶのピークが鋭く現れ、低エネルギー側のスペクトルの裾野が下がっているＭＣＡスペクトルが得られた。
(Example 2)
Next, the (111) B surface of the same CdZnTe substrate as in Example 1 was subjected to plasma etching with Ar gas to remove the work-affected layer on the surface. Thereafter, a mask having an opening in the shape of a pixel electrode pattern is formed on the B surface, the substrate is set in a vacuum evaporation furnace, and In is deposited on the B surface exposed from the opening of the mask to a thickness of 300 nm. A plurality of pixel-shaped Schottky electrodes were formed. Then, the inside of the furnace was evacuated and the substrate was annealed at 200 ° C. Thereafter, Pt was deposited on the entire (111) A surface of the substrate by electroless plating to a thickness of 50 nm to form an ohmic electrode.
When the change in the composition in the direction perpendicular to the B-plane at the junction between the substrate and the Schottky electrode in the sample of the example prepared as described above was examined by energy dispersive X-ray fluorescence analysis, it was the same as in Example 1. A graph in which the oxygen concentration in the interface vicinity region T is less than 1 at% was obtained.
Then, when a radiation detector was configured using the sample of this example, and this radiation detector was irradiated with radiation using Co57 as a radiation source, a peak of 122.2 keV similar to that of Example 1 appeared sharply, and low An MCA spectrum in which the base of the spectrum on the energy side was lowered was obtained.
（比較例）
次に、実施例１，２と同じＣｄＺｎＴｅ基板（１１１）Ｂ面に臭素（Ｂｒ）とメタノールとの混合溶液でエッチングを行って表面の加工変質層を除去した。この臭素-メタノール混合溶液はＣｄＺｎＳｅＴｅ等の化合物半導体では表面処理によく使われるエッチャントである。この前処理後、基板を真空蒸着炉内にセットし、Ｂ面にＩｎを厚さ３００ｎｍ蒸着してショットキー電極を形成した。そして、炉内を真空引きし、基板を２００℃でアニールした。その後、基板の（１１１）Ａ面に無電解めっきでＰｔを厚さ５０ｎｍとなるまで析出させオーミック電極を形成した。
このようにして作成した比較例サンプルの基板とショットキー電極との接合部における、Ｂ面と直交する方向の組成の変化をエネルギー分散型蛍光Ｘ線分析法で調べたところ、図３（ｂ），（ｃ）に示すグラフが得られた。このグラフからは、界面近傍領域Ｔ（起点Ｏから約２〜３２ｎｍ）において酸素濃度が１ａｔ％以上の領域が多く見られること、特に当該領域Ｔのショットキー電極近傍（起点Ｏから２３〜２４ｎｍ付近）では３ａｔ％にまで達していることが見て取れる。
そして、この比較例サンプルを用いて放射線検出器を構成し、この放射線検出器にＣｏ５７を放射線源とする放射線を照射したところ、図４（ｂ）に示すＭＣＡスペクトルが得られた。このスペクトルからは、１２２．２ｋｅＶに鋭いピークは見られず、低エネルギーの肩に盛り上がりがあることが見て取れる。なお、このピークの印加電圧５００Ｖにおける半値幅は７．０％と高かった。
(Comparative example)
Next, etching was performed on the same CdZnTe substrate (111) B surface as in Examples 1 and 2 with a mixed solution of bromine (Br) and methanol to remove the work-affected layer on the surface. This bromine-methanol mixed solution is an etchant often used for surface treatment in a compound semiconductor such as CdZnSeTe. After this pretreatment, the substrate was set in a vacuum evaporation furnace, and a 300 nm thick In was evaporated on the B surface to form a Schottky electrode. Then, the inside of the furnace was evacuated and the substrate was annealed at 200 ° C. Thereafter, Pt was deposited on the (111) A surface of the substrate by electroless plating to a thickness of 50 nm to form an ohmic electrode.
When the change in the composition in the direction orthogonal to the B-plane at the junction between the substrate of the comparative example sample thus prepared and the Schottky electrode was examined by energy dispersive X-ray fluorescence analysis, FIG. The graph shown in (c) was obtained. From this graph, it can be seen that there are many regions where the oxygen concentration is 1 at% or more in the interface vicinity region T (about 2 to 32 nm from the origin O), especially in the vicinity of the Schottky electrode in the region T (from 23 to 24 nm from the origin O). ), It can be seen that it has reached 3 at%.
Then, a radiation detector was configured using this comparative sample, and when this radiation detector was irradiated with radiation using Co57 as a radiation source, the MCA spectrum shown in FIG. 4B was obtained. From this spectrum, it can be seen that there is no sharp peak at 122.2 keV and there is a rise in the shoulder of low energy. The full width at half maximum at an applied voltage of 500 V at this peak was as high as 7.0%.
上記実験から、本実施形態のように、基板１のＢ面（他方の主面）１ｂを、酸素を含まないエッチングガスを用いてドライエッチングし、その後、基板１を非酸化性雰囲気に晒したまま、Ｂ面１ｂにショットキー電極（第２電極）３を形成し、基板１とショットキー電極３との接合部のうち、境界近傍領域Ｔ（Ｉｎ（第２電極を構成する元素）の濃度が５０％となる箇所からＢ面１ｂと直交する方向に±１５ｎｍの範囲）における酸素濃度が１原子％以下となるようにすることにより、放射線計数スペクトルの低エネルギー側の持ち上がりを従来よりも少なくでき、その分だけピークを鋭く（半値幅を小さく）できることが判明した。スペクトルのピークが鋭いほど、放射線検出素子のエネルギー分解能が高いことを示すので、本実施形態の放射線検出素子は、従来のものに比べ、高い精度で放射線を検出することができるということになる。なお、プラズマエッチングによる表面処理は、基板表面の結晶構造を破壊してしまうことが懸念されたが、今回の実験では、良好な放射線検出特性が得られたことから、表面へのダメージはないか、あっても素子特性に影響のない無視できるレベルであることが分かった。 From the above experiment, as in this embodiment, the B surface (the other main surface) 1b of the substrate 1 was dry-etched using an etching gas not containing oxygen, and then the substrate 1 was exposed to a non-oxidizing atmosphere. The Schottky electrode (second electrode) 3 is formed on the B surface 1b as it is, and the concentration in the vicinity of the boundary T (In (element constituting the second electrode)) in the junction between the substrate 1 and the Schottky electrode 3 By increasing the oxygen concentration in the range of ± 15 nm in the direction perpendicular to the B-plane 1b from the point where the value is 50%), the radiation count spectrum has less lift on the low energy side than before. It was found that the peak can be sharpened by that much (half-value width is reduced). The sharper the peak of the spectrum, the higher the energy resolution of the radiation detection element. Therefore, the radiation detection element of this embodiment can detect radiation with higher accuracy than the conventional one. In addition, there was concern that the surface treatment by plasma etching would destroy the crystal structure of the substrate surface, but in this experiment, good radiation detection characteristics were obtained, so there was no damage to the surface. It was found that the level was negligible without affecting the device characteristics.
以上、本発明を実施形態に基づいて具体的に説明してきたが、本発明は上記実施形態に限定されるものではなく、その要旨を逸脱しない範囲で変更可能である。
例えば、上記実施形態では、Ａ面にオーミック電極を形成し、Ｂ面にショットキー電極を形成した素子について説明したが、Ａ面にショットキー電極を形成し、Ｂ面にオーミック電極を形成したものとしてもよい。
また、上記実施形態では、オーミック電極をＡ面全体を覆うように形成したものとしたが、Ｂ面全体を覆うようなショットキー電極を形成する場合には、オーミック電極を複数のピクセル状のものとしてもよい。
また、上記実施形態では、基板の鏡面研磨の後、直ちにドライエッチングを行ったが、ウェットエッチングを行った後、更にドライエッチングを行うようにしてもよい。
また、上記実施形態では、ショットキー電極を形成した後にオーミック電極を形成するようにしたが、オーミック電極を形成した後にショットキー電極を形成するようにしてもよい。
As mentioned above, although this invention was concretely demonstrated based on embodiment, this invention is not limited to the said embodiment, It can change in the range which does not deviate from the summary.
For example, in the above-described embodiment, the element in which the ohmic electrode is formed on the A surface and the Schottky electrode is formed on the B surface has been described. However, the Schottky electrode is formed on the A surface and the ohmic electrode is formed on the B surface. It is good.
In the above embodiment, the ohmic electrode is formed so as to cover the entire A surface. However, in the case of forming a Schottky electrode that covers the entire B surface, the ohmic electrode has a plurality of pixel shapes. It is good.
In the above embodiment, dry etching is performed immediately after mirror polishing of the substrate. However, dry etching may be performed after wet etching.
In the above embodiment, the ohmic electrode is formed after the Schottky electrode is formed. However, the Schottky electrode may be formed after the ohmic electrode is formed.
１０ 放射線検出素子
１ 基板
１ａ Ａ面（一方の主面）
１ｂ Ｂ面（他方の主面）
２ オーミック電極（第１電極）
３ ショットキー電極（第２電極）
10 Radiation detection element 1 Board | substrate 1a A surface (one main surface)
1b B surface (the other main surface)
2 Ohmic electrode (first electrode)
3 Schottky electrode (second electrode)
Claims (2)
前記基板と前記第２電極との接合部のうち、前記第２電極を構成する元素の濃度が５０％となる箇所から前記他方の主面と直交する方向に±１５ｎｍの範囲における酸素濃度が１原子％以下となっていることを特徴とする放射線検出素子。 A substrate, a first electrode formed on one main surface of the substrate so as to be in ohmic contact with the substrate, and a first electrode formed on the other main surface of the substrate so as to be Schottky bonded with the substrate. A radiation detection element comprising two electrodes,
Of the junction between the substrate and the second electrode, the oxygen concentration in the range of ± 15 nm in a direction perpendicular to the other main surface from a portion where the concentration of the element constituting the second electrode is 50% is 1 A radiation detecting element characterized in that it is at most atomic%.
前記基板の他方の主面を、酸素を含まないエッチングガスを用いてドライエッチングし、
その後、前記基板を非酸化性雰囲気に晒したまま、前記他方の主面に前記第２電極を形成することを特徴とする放射線検出素子の製造方法。 A substrate, a first electrode formed on one main surface of the substrate so as to be in ohmic contact with the substrate, and a first electrode formed on the other main surface of the substrate so as to be Schottky bonded with the substrate. In a method for manufacturing a radiation detection element comprising two electrodes,
The other main surface of the substrate is dry-etched using an etching gas not containing oxygen,
Thereafter, the second electrode is formed on the other main surface while the substrate is exposed to a non-oxidizing atmosphere.
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