JPH04356977A - Porous silicon - Google Patents
Porous siliconInfo
- Publication number
- JPH04356977A JPH04356977A JP3198668A JP19866891A JPH04356977A JP H04356977 A JPH04356977 A JP H04356977A JP 3198668 A JP3198668 A JP 3198668A JP 19866891 A JP19866891 A JP 19866891A JP H04356977 A JPH04356977 A JP H04356977A
- Authority
- JP
- Japan
- Prior art keywords
- porous silicon
- silicon
- light
- light emitting
- porous
- 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
Links
- 229910021426 porous silicon Inorganic materials 0.000 title claims abstract description 89
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910052710 silicon Inorganic materials 0.000 claims abstract description 20
- 239000010703 silicon Substances 0.000 claims abstract description 20
- 239000000758 substrate Substances 0.000 claims abstract description 18
- 239000013078 crystal Substances 0.000 claims abstract description 12
- 239000010410 layer Substances 0.000 claims description 24
- 238000011282 treatment Methods 0.000 claims description 13
- 238000004519 manufacturing process Methods 0.000 claims description 9
- 238000005530 etching Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 6
- 239000002344 surface layer Substances 0.000 claims description 6
- 238000007743 anodising Methods 0.000 claims description 4
- 230000001678 irradiating effect Effects 0.000 claims description 4
- 238000003486 chemical etching Methods 0.000 claims description 3
- 238000006243 chemical reaction Methods 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 239000000463 material Substances 0.000 abstract description 10
- 238000011161 development Methods 0.000 abstract description 2
- 239000011148 porous material Substances 0.000 abstract 2
- 230000003287 optical effect Effects 0.000 description 12
- 238000005424 photoluminescence Methods 0.000 description 11
- 238000002048 anodisation reaction Methods 0.000 description 9
- 239000004065 semiconductor Substances 0.000 description 8
- 230000015572 biosynthetic process Effects 0.000 description 7
- 238000000295 emission spectrum Methods 0.000 description 7
- 239000007864 aqueous solution Substances 0.000 description 6
- 238000010586 diagram Methods 0.000 description 6
- 239000008204 material by function Substances 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 238000001194 electroluminescence spectrum Methods 0.000 description 3
- 230000003595 spectral effect Effects 0.000 description 3
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 3
- 229910052721 tungsten Inorganic materials 0.000 description 3
- 239000010937 tungsten Substances 0.000 description 3
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 230000005284 excitation Effects 0.000 description 2
- 239000007788 liquid Substances 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 230000005693 optoelectronics Effects 0.000 description 2
- 230000010355 oscillation Effects 0.000 description 2
- 230000035945 sensitivity Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 229910052681 coesite Inorganic materials 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 229910052906 cristobalite Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000001514 detection method Methods 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000011156 evaluation Methods 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000002739 metals Chemical class 0.000 description 1
- 238000000034 method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 230000000149 penetrating effect Effects 0.000 description 1
- 238000000103 photoluminescence spectrum Methods 0.000 description 1
- 238000001020 plasma etching Methods 0.000 description 1
- 229920001296 polysiloxane Polymers 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 229910021332 silicide Inorganic materials 0.000 description 1
- FVBUAEGBCNSCDD-UHFFFAOYSA-N silicide(4-) Chemical compound [Si-4] FVBUAEGBCNSCDD-UHFFFAOYSA-N 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 235000012239 silicon dioxide Nutrition 0.000 description 1
- 239000002210 silicon-based material Substances 0.000 description 1
- 230000005476 size effect Effects 0.000 description 1
- 229910052682 stishovite Inorganic materials 0.000 description 1
- 229910052905 tridymite Inorganic materials 0.000 description 1
Landscapes
- Weting (AREA)
- Semiconductor Lasers (AREA)
- Light Receiving Elements (AREA)
- Led Devices (AREA)
Abstract
Description
【０００１】0001
【産業上の利用分野】この発明は、多孔質シリコンに関
するものである。さらに詳しくは、この発明は、可視光
域での発光や受発光機能を有する光機能素子等として有
用な多孔質シリコンに関するものである。FIELD OF THE INVENTION This invention relates to porous silicon. More specifically, the present invention relates to porous silicon which is useful as an optical functional element having a function of emitting light and receiving and emitting light in the visible light range.
【０００２】0002
【従来の技術とその課題】従来より、各種の組成と構造
からなる受光素子や発光素子等の光機能材料、そして、
それらのデバイスが知られているが、半導体材料からな
る光素子としては、ＧａＡｓ系の化合物半導体などの極
めて限定された種類のものしか知られていない。[Prior Art and its Problems] Conventionally, optical functional materials such as light-receiving elements and light-emitting elements having various compositions and structures, and
Although these devices are known, only extremely limited types of optical elements made of semiconductor materials, such as GaAs-based compound semiconductors, are known.
【０００３】光エレクトロニクスのデバイス材料として
は、小型で、かつ、高効率での受・発光が可能な半導体
材料の出現が望まれているところであるが、前記の通り
の限られた種類の化合物半導体がこのような機能を有す
るものとして知られているにすぎない。しかも、これら
の化合物半導体はその製造が難しく、高コストであって
、組成の均質性、素子構成の厳密性を確保しなければな
らないことから、これまでに実用化されている半導体レ
ーザー等においても、その製造は簡便ではなく、また、
生産コストの低減にも大きな制約があった。As device materials for optoelectronics, there is a desire for semiconductor materials that are compact and capable of receiving and emitting light with high efficiency. However, as mentioned above, there are limited types of compound semiconductors. is only known as having such a function. Moreover, these compound semiconductors are difficult to manufacture and expensive, and it is necessary to ensure homogeneity of composition and strictness of device configuration. , its production is not simple, and
There were also major constraints on reducing production costs.
【０００４】このような観点から、たとえばシリコン等
の最も一般的な半導体材料についても受発光等の光機能
の実現が研究の対象として考慮されてきたが、これまで
のところ、この出願の発明者の検討以外にはほとんどそ
の可能性を示唆する報告や提案はなされていないのが実
情である。この発明は、以上の通りの事情に鑑みてなさ
れたものであり、受光・発光素子等の光機能材料の新し
い展開を可能とする新規なシリコン材料を提供すること
を目的としている。From this point of view, the realization of optical functions such as reception and emission of light and reception has been considered as a subject of research for the most common semiconductor materials such as silicon, but so far, the inventor of this application The reality is that there have been almost no reports or proposals suggesting this possibility other than consideration of this possibility. This invention was made in view of the above circumstances, and aims to provide a new silicon material that enables new development of optical functional materials such as light receiving and light emitting devices.
【０００５】[0005]
【課題を解決するための手段】この発明は、上記の課題
を解決するものとして、シリコン単結晶の基板表面に微
小孔を有する多孔質シリコンからなる発光多孔質シリコ
ンとその素子、そしてその製造法を提供する。また、こ
の発明は、この発光とともに、可視光受光をも可能とす
る新しい受発光多孔質シリコンをも提供する。[Means for Solving the Problems] The present invention solves the above problems by providing a light-emitting porous silicon made of porous silicon having micropores on the surface of a silicon single crystal substrate, a device thereof, and a method for manufacturing the same. I will provide a. The present invention also provides a new light-emitting/receiving porous silicon that is capable of receiving visible light as well as emitting light.
【０００６】すなわち、この発明は、この出願の発明者
によって検討されてきたシリコン半導体材料の機能高度
化のアプローチの過程において見出された画期的な知見
に基づくものであって、シリコン単結晶の基板表面に多
数の、たとえば約２〜５０ｎｍ径の微小孔を形成した多
孔質シリコンからなる発光多孔質シリコンという特異的
な光機能材料を提供し、また、この材料が受光素子とし
ても使用し得るとの知見も加え、新しい受発光素子等も
提供するものである。[0006] That is, the present invention is based on the groundbreaking knowledge discovered in the course of the approach to functional advancement of silicon semiconductor materials that has been studied by the inventor of this application. We provide a unique optically functional material called luminescent porous silicon, which is made of porous silicon in which many micropores, for example, approximately 2 to 50 nm in diameter, are formed on the surface of a substrate, and this material can also be used as a light receiving element. In addition to the knowledge that will be obtained, we will also provide new light-receiving and emitting devices.
【０００７】この発明の多孔質シリコンは、たとえば図
１に模式的に示したように、シリコン単結晶基板（１）
に、微小孔（２）が形成されているものであって、その
微小孔（２）の平均直径は、たとえば２〜５０ｎｍ程度
の大きさを有している。この微小孔（２）を有する多孔
質シリコン（ＰＳ）層（３）は、たとえば陽極化成する
ことによって形成できるものであって、シリコン単結晶
をＨＦ水溶液中等で処理することによって形成すること
ができる。The porous silicon of the present invention can be used, for example, as schematically shown in FIG.
Micropores (2) are formed therein, and the average diameter of the micropores (2) is, for example, about 2 to 50 nm. This porous silicon (PS) layer (3) having micropores (2) can be formed, for example, by anodization, and can be formed by treating a silicon single crystal with an HF aqueous solution or the like. .
【０００８】ｐ型あるいはｎ型のいずれの場合でもこの
微小孔（２）を有する多孔質シリコン（ＰＳ）層（３）
の形成は可能であって、前記の微小孔（２）の平均直径
は、シリコン単結晶基板（１）の比抵抗と陽極化成の条
件等によって変化させることができる。このような微小
孔（２）の形成は、金属の孔食と似ており、直径ととも
に、その多孔質シリコン（ＰＳ）層（３）の厚み（ｄ）
は、化成時間等の条件の選択によって、たとえば約１〜
１００ μｍ程度の範囲で広範囲に制御することができ
る。
多孔度は、ほぼ２０〜８０％程度とすることができ、基
板の比抵抗と化成条件等によって選択することができる
。そして、表面積は、体積比として、２００ ｍ２ ／
ｃｍ３ 程度にまで及ぶ。A porous silicon (PS) layer (3) having micropores (2), whether p-type or n-type.
The average diameter of the micropores (2) can be changed depending on the specific resistance of the silicon single crystal substrate (1), the conditions of anodization, etc. The formation of such micropores (2) is similar to pitting corrosion in metals, and the thickness (d) of the porous silicon (PS) layer (3) as well as the diameter
is, for example, about 1 to 1, depending on the selection of conditions such as formation time.
It can be controlled over a wide range of about 100 μm. The porosity can be approximately 20 to 80%, and can be selected depending on the resistivity of the substrate, chemical formation conditions, etc. And the surface area is 200 m2 / as a volume ratio.
It extends to about cm3.
【０００９】このような多孔質シリコン（ＰＳ）層（３
）は、高抵抗率で、１０１１Ωｃｍ以上の抵抗値を有し
、また、酸化によって厚いＳｉＯ２ 層を形成すること
ができるという特質を有してもいる。多孔質シリコン（
ＰＳ）については、ＳＯＩ構造の形成、ヘテロエピタシ
ー、シリサイド形成、あるいは湿式太陽電池への応用が
研究されてきているが、光電子特性については、この出
願の発明者以外によっては検討されてきていない。[0009] Such a porous silicon (PS) layer (3
) has a high resistivity, with a resistance value of 1011 Ωcm or more, and also has the characteristic that a thick SiO2 layer can be formed by oxidation. Porous silicon (
Regarding PS), the formation of SOI structure, heteroepitasy, silicide formation, and application to wet solar cells have been studied, but the optoelectronic properties have not been studied by anyone other than the inventor of this application. .
【００１０】この発明は、発明者のこれまでの検討から
得られた知見を踏まえつつ、多孔質シリコン（ＰＳ）に
よる発光機能と可視部における受光機能というさらに新
たな発見に基づいて完成されている。発光、受光機能を
有するこの発明の多孔質シリコンについてさらに説明す
ると、図１に示したような基板（１）表面に多孔質シリ
コン（ＰＳ）層（３）を有する構造は、前記した通りの
陽極化成によって形成できるとともに、この多孔質シリ
コン層（３）の微小孔（２）の大きさ（径）や深さを、
前記の通り化成条件等のコントロールによって変化させ
ることや、さらには、多孔質シリコン層（３）の表面層
（〜１００ Å程度）をエッチング処理することによっ
て、表面層を除去し、前記の構造を安定化したり、微小
孔（２）の形状、大きさ等をより効果的に制御すること
ができる。[0010] This invention was completed based on the knowledge obtained from the inventor's previous studies, and based on the new discovery of the light-emitting function and light-receiving function in the visible region of porous silicon (PS). . To further explain the porous silicon of the present invention having light emitting and light receiving functions, the structure having a porous silicon (PS) layer (3) on the surface of a substrate (1) as shown in FIG. It can be formed by chemical formation, and the size (diameter) and depth of the micropores (2) of this porous silicon layer (3) can be controlled.
As mentioned above, by controlling the chemical formation conditions, etc., and by etching the surface layer (about 100 Å) of the porous silicon layer (3), the surface layer is removed and the above structure is changed. It is possible to stabilize the shape, size, etc. of the micropores (2) more effectively.
【００１１】これらの制御によって、発光波長の変更、
調整もこの発明によって可能となる。微小孔（２）の制
御は、いわゆる量子サイズ効果をも実現する。表面層の
エッチング処理としては、化学エッチング、プラズマエ
ッチング等の適宜な手段が採用できる。たとえば化学エ
ッチングとして、陽極化成処理後の多孔質シリコンの表
面をＫＯＨ水溶液に浸して行なうことができる。酸素ガ
ス等を使用してもよい。[0011] Through these controls, the emission wavelength can be changed,
Adjustment is also possible with this invention. Control of the micropores (2) also realizes the so-called quantum size effect. As the etching treatment for the surface layer, appropriate means such as chemical etching and plasma etching can be employed. For example, chemical etching can be performed by immersing the surface of porous silicon after anodization treatment in a KOH aqueous solution. Oxygen gas or the like may also be used.
【００１２】また、化成処理中に、光を照射し、たとえ
ば２００ 〜３００ μＡ／ｃｍ２ 程度の短絡電流を
通電することによって処理することもできる。これらの
処理を可能とするこの発明の多孔質シリコンは、多孔質
層を持たないシリコン基板と一体のものとして光素子や
その他の光機能材としてもよいし、あるいは、多孔質層
のみからなる、すなわち貫通微小孔を有する多孔質シリ
コン板として使用してもよい。Further, during the chemical conversion treatment, the treatment can also be carried out by irradiating light and passing a short circuit current of, for example, about 200 to 300 μA/cm 2 . The porous silicon of the present invention, which enables these treatments, may be used as an optical element or other optical functional material as an integral part with a silicon substrate that does not have a porous layer, or it may be made of only a porous layer. That is, it may be used as a porous silicon plate having through-holes.
【００１３】この後者の場合には、陽極化成、さらには
必要に応じてエッチング処理した後に、多孔質シリコン
層を剥離して使用することができる。より具体的には、
ＨＦ中の陽極化成において、電流を電解研磨の水準（≧
４００ ｍＡ／ｃｍ２ ）程度までに一挙に増大させる
。こうすることによって、多孔質シリコン層のみがＨＦ
液面に浮いてくるので、これをすくい上げて濾紙上で乾
燥する。In the latter case, the porous silicon layer can be peeled off and used after anodization and, if necessary, etching treatment. More specifically,
During anodization in HF, the current is adjusted to the level of electrolytic polishing (≧
400 mA/cm2). By doing this, only the porous silicon layer is exposed to HF.
It will float to the surface of the liquid, so scoop it up and dry it on filter paper.
【００１４】このようにして単離された多孔質シリコン
は、適宜に積層構造化し、デバイスとして応用される。
たとえば以上の通りの、基板表面部に微小孔を有する多
孔質シリコン、あるいは貫通孔を有する多孔質シリコン
のいずれのものも、光機能材として有用であり、たとえ
ばＥＬ素子、ＬＥＤ、ＬＤ、さらには光励起によるレー
ザ発振装置、ＯＥＩＣ等として優れた作用効果を発揮す
る。The porous silicon thus isolated is appropriately formed into a layered structure and applied as a device. For example, as described above, porous silicon having micropores on the surface of the substrate or porous silicon having through holes are useful as optical functional materials, such as EL elements, LEDs, LDs, and even porous silicones having through holes. It exhibits excellent effects as a laser oscillation device using optical excitation, OEIC, etc.
【００１５】以下、実施例を示し、さらに詳しくこの発
明のシリコン光素子について説明する。[0015] Hereinafter, the silicon optical device of the present invention will be explained in more detail by way of examples.
【００１６】[0016]
実施例１
裏面にオーミックコンタクト（Ａｌ）をとったｐ型Ｓｉ
ウェハー（８〜１１Ω・ｃｍ）を、その一部表面を露出
させて耐酸性ワックスで被覆した後にＨＦ水溶液（２０
〜４８ｗｔ％ ）中で陽極化成（２５〜８０ｍＡ／ｃｍ
２ ）処理し、シリコン単結晶基板表面に多孔性の微小
孔を有する多孔質シリコン（ＰＳ）層を形成した。その
厚さは、約４０μｍであって、平均直径は、およそ１２
ｎｍであった。Example 1 P-type Si with ohmic contact (Al) on the back side
A wafer (8 to 11 Ω cm) was coated with acid-resistant wax with a part of its surface exposed, and then treated with an HF aqueous solution (20
~48wt%) in anodization (25~80mA/cm
2) A porous silicon (PS) layer having porous micropores was formed on the surface of the silicon single crystal substrate. Its thickness is approximately 40 μm and its average diameter is approximately 12
It was nm.
【００１７】この多孔質シリコン（ＰＳ）に対して、水
銀ランプを用いて赤外線成分をフィルター除去したＵＶ
光を照射した。温度は室温とした。その結果、たとえば
図２に例示した通りのホトルミネッセンスの発光スペク
トルを得た。ピーク波長は７５００Åで、発光色は橙色
あった。なお、陽極化成には、対向電極としてＰｔを使
用した。This porous silicon (PS) is exposed to UV light by using a mercury lamp to filter out infrared components.
irradiated with light. The temperature was room temperature. As a result, a photoluminescence emission spectrum as illustrated in FIG. 2, for example, was obtained. The peak wavelength was 7500 Å, and the emission color was orange. In addition, Pt was used as a counter electrode for anodization.
【００１８】実施例２
実施例１と同様にして陽極化成し、多孔質シリコンを作
製した。電流をより大きくする場合、ＨＦ濃度を低下さ
せる場合、さらにはシリコン基板としてより大きな比抵
抗のものを用いる場合には、ホトルミネッセンスの発光
スペクトルはより短波長の青色発光にシフトすることが
確認された。Example 2 Porous silicon was produced by anodization in the same manner as in Example 1. It has been confirmed that when increasing the current, decreasing the HF concentration, or using a silicon substrate with a higher resistivity, the photoluminescence emission spectrum shifts to blue light with a shorter wavelength. Ta.
【００１９】実施例３
実施例１と同様にして、抵抗値８〜１１Ω・ｃｍのｐ型
Ｓｉウェハーおよび比抵抗１〜２Ω・ｃｍのｎ型Ｓｉウ
ェハーを陽極化成処理した。この場合の電流は、ｐ型の
時には２５ｍＡ／ｃｍ２ 、ｎ型の時には８０ｍＡ／ｃ
ｍ２ とした。また、いずれの場合もＨＦ水溶液の濃度
は、４８％とした。ｎ型の場合には、距離２０ｃｍにお
いて５００ Ｗタングステンランプによる光照射を行な
った。Example 3 In the same manner as in Example 1, a p-type Si wafer having a resistance value of 8 to 11 Ω·cm and an n-type Si wafer having a specific resistance of 1 to 2 Ω·cm were anodized. In this case, the current is 25mA/cm2 for p-type and 80mA/cm2 for n-type.
m2. Further, in both cases, the concentration of the HF aqueous solution was 48%. In the case of n-type, light irradiation was performed with a 500 W tungsten lamp at a distance of 20 cm.
【００２０】各々、４０μｍ厚の多孔質層を有するｐ型
多孔質シリコンとｎ型多孔質シリコンを得た。この各々
の多孔質シリコンについてＮ２ レーザーを照射し、室
温でのホトルミネッセンス特性を確認した。また、５０
０ ＷＸｅランプを使用し、フィルター処理したＵＶ光
を照射し、室温でのホトルミネッセンススペクトルを測
定した。その結果を示したものが図３である。P-type porous silicon and n-type porous silicon each having a porous layer with a thickness of 40 μm were obtained. Each porous silicon was irradiated with N2 laser and its photoluminescence characteristics at room temperature were confirmed. Also, 50
A 0 WXe lamp was used to irradiate filtered UV light and measure the photoluminescence spectra at room temperature. FIG. 3 shows the results.
【００２１】ｐ型多孔質シリコンでは約７００ｎｍ に
ピークが見られ、また、ｎ型多孔質シリコンでは、約６
５０ｎｍ （黄色）にピークが確認された。
実施例４
実施例３において作製したｐ型多孔質シリコンをＫＯＨ
１０％（ｍｔ）水溶液に浸し、表面の化学エッチングを
行なった。[0021] In p-type porous silicon, a peak is seen at about 700 nm, and in n-type porous silicon, a peak is observed at about 600 nm.
A peak was observed at 50 nm (yellow). Example 4 The p-type porous silicon produced in Example 3 was heated with KOH.
The surface was chemically etched by immersing it in a 10% (mt) aqueous solution.
【００２２】この処理により、乾燥時の表面層と多孔質
シリコン層内部との界面ストレスによる損傷が効果的に
防止された。また、この処理により発光強度はより大き
くなり、ホトルミネッセンス発光スペクトルの青色側へ
のシフトも認められた。
実施例５
実施例３のｐ型多孔質シリコンの作製において、５００
Ｗタングステンランプを用いて、距離２０ｃｍで光照
射しつつ陽極化成を行なった。This treatment effectively prevented damage due to interfacial stress between the surface layer and the inside of the porous silicon layer during drying. Furthermore, this treatment increased the emission intensity, and a shift of the photoluminescence emission spectrum toward the blue side was also observed. Example 5 In the production of p-type porous silicon in Example 3, 500
Anodization was performed using a W tungsten lamp while irradiating light at a distance of 20 cm.
【００２３】得られた多孔質シリコンのＸｅランプＵＶ
によるホトルミネッセンスは、図３に示したように、室
温で６２０ｎｍ にスペクトルピークを有する黄色であ
ることが確認された。なお、化成処理中に、短絡電流（
２００ 〜３００ μＡ／ｃｍ２ ）を約２〜５分流す
ことにより表層部のエッチングが進行し、発光強度がよ
り大きくなること、さらにスペクトルの青色側へのシフ
トが確認された。Xe lamp UV of the obtained porous silicon
As shown in Figure 3, the photoluminescence caused by the photoluminescence was confirmed to be yellow with a spectral peak at 620 nm at room temperature. In addition, during chemical conversion treatment, short circuit current (
By flowing 200 to 300 μA/cm2) for about 2 to 5 minutes, etching of the surface layer proceeded, and it was confirmed that the emission intensity became higher and that the spectrum shifted to the blue side.
【００２４】実施例６
実施例５と同様にして作製したｐ型多孔質シリコンを、
さらに酸素雰囲気下において熱処理した。得られた多孔
質シリコン（Ａ）を、陽極化成処理のみしたｐ型多孔質
シリコン（Ｂ）と対比しつつ、そのホトルミネッセンス
発光スペクスルを示したものが図４である。励起光とし
ては、Ｈｅ−Ｃｄレーザー（３２５ｎｍ）を使用した。
ピーク５００ｎｍ の青色のホトルミネッセンスを確認
した。Example 6 P-type porous silicon produced in the same manner as in Example 5 was
Further, heat treatment was performed in an oxygen atmosphere. FIG. 4 shows the photoluminescence emission spectrum of the obtained porous silicon (A) in comparison with the p-type porous silicon (B) which was only subjected to anodizing treatment. A He-Cd laser (325 nm) was used as excitation light. Blue photoluminescence with a peak of 500 nm was confirmed.
【００２５】実施例７
ｐ型Ｓｉウェハー（１１１ ）（１０〜２０Ω・ｃｍ）
を用い、電流；１０ｍＡ／ｃｍ２ およびＨＦ濃度；２
０％の条件において陽極化成し、多孔質層の厚さ３μｍ
の多孔質シリコンを得た。これを５００ Ｗタングステ
ンランプで照射しつつ、ＨＦ水溶液中において短絡電流
（２００ μＡ／ｃｍ２ ）通電し、エッチング処理し
た。Example 7 P-type Si wafer (111) (10-20Ωcm)
using current: 10 mA/cm2 and HF concentration: 2
Anodized under 0% condition, porous layer thickness 3μm
Porous silicon was obtained. While irradiating this with a 500 W tungsten lamp, a short circuit current (200 μA/cm 2 ) was applied in an HF aqueous solution to perform etching treatment.
【００２６】図５に示したように、この多孔質シリコン
層（ＰＳ）を有するｐ型シリコン基板の片面にＡｌ層を
、また他面に半透明電極として１５０ Å厚のＡｕを配
設し、順方向電圧１７．５Ｖを印加した（電流１００
ｍＡ／ｃｍ２ ）。室温において、図６に示したＥＬス
ペクトルが確認された。ロックイン検出（チョッパ周波
数１３０ Ｈｚ）とした。As shown in FIG. 5, an Al layer was disposed on one side of the p-type silicon substrate having the porous silicon layer (PS), and a 150 Å thick Au layer was disposed on the other side as a semi-transparent electrode. A forward voltage of 17.5 V was applied (current 100
mA/cm2). At room temperature, the EL spectrum shown in FIG. 6 was confirmed. Lock-in detection (chopper frequency 130 Hz) was used.
【００２７】実施例８
ｐ型多孔質シリコン（多孔質層厚み、３０μｍ）（基板
８〜１１Ω・ｃｍ）を用意し、その側面に図７に示した
ように半透明電極としてＡｕ蒸着し、基板側が負（−）
となるように電圧を印加し、Ｘｅランプ（５００ Ｗ）
を光源として光照射した。Example 8 A p-type porous silicon (porous layer thickness: 30 μm) (substrate: 8 to 11 Ω·cm) was prepared, and Au was deposited on the side surface as a semitransparent electrode as shown in FIG. Negative (-) side
Apply voltage so that
was used as a light source.
【００２８】その結果、図８に示したように、多孔質シ
リコン（ＰＳ）層には、その分光感度に明確な電圧依存
性が確認された。また、基礎吸収端が可視部にあること
も確認された。このことから、この多孔質シリコン（Ｐ
Ｓ）光は、可視部の受光素子としても有効であることが
わかる。As a result, as shown in FIG. 8, a clear voltage dependence in the spectral sensitivity of the porous silicon (PS) layer was confirmed. It was also confirmed that the fundamental absorption edge is in the visible region. From this, this porous silicon (P
S) It can be seen that light is also effective as a light receiving element in the visible region.
【００２９】実施例９
実施例３において、陽極化成処理中に、電流を電解研磨
水準（３２０ ｍＡ／ｃｍ２ ）にまで一挙に増大させ
た。その結果、ｐ型多孔質シリコン層のみが剥離されて
ＨＦ液面上に浮上した。これをすくい上げて濾紙上で乾
燥した。Example 9 In Example 3, the current was suddenly increased to the electrolytic polishing level (320 mA/cm2) during the anodizing treatment. As a result, only the p-type porous silicon layer was peeled off and floated on the HF liquid surface. This was scooped up and dried on filter paper.
【００３０】この貫通微小孔を有する多孔質シリコン板
について、Ｘ線回折評価を行なった。図９に示したよう
に、単結晶性を保っていることが確認された。[0030] X-ray diffraction evaluation was performed on this porous silicon plate having penetrating micropores. As shown in FIG. 9, it was confirmed that single crystallinity was maintained.
【００３１】[0031]
【発明の効果】この発明によって、以上詳しく説明した
通り、シリコン半導体によって全く新しい光機能材料、
たとえば発光素子、さらには受光素子等としてのＥＬ、
ＬＥＤ、ＬＤ、レーザー発振装置ＯＥＩＣ等が実現され
る。[Effects of the Invention] As explained in detail above, this invention enables completely new optical functional materials to be created using silicon semiconductors.
For example, EL as a light emitting element, furthermore, a light receiving element, etc.
LED, LD, laser oscillation device OEIC, etc. will be realized.
【図１】この発明の多孔質シリコン（ＰＳ）光素子を模
式的に例示した断面図である。FIG. 1 is a cross-sectional view schematically illustrating a porous silicon (PS) optical device of the present invention.
【図２】この発明の多孔質シリコン（ＰＳ）素子による
ホトルミネッセンス発光スペクトルを示したスペクトル
図である。FIG. 2 is a spectrum diagram showing the photoluminescence emission spectrum of the porous silicon (PS) element of the present invention.
【図３】この発明の別の多孔質シリコン（ＰＳ）による
ホトルミネッセンス発光スペクトル図である。FIG. 3 is a photoluminescence emission spectrum diagram of another porous silicon (PS) of the present invention.
【図４】さらに別の多孔質シリコン（ＰＳ）のホトルミ
ネッセンス発光スペクトル図である。FIG. 4 is a photoluminescence emission spectrum diagram of yet another porous silicon (PS).
【図５】ＥＬスペクトル測定用デバイスの断面図である
。FIG. 5 is a cross-sectional view of an EL spectrum measurement device.
【図６】ＥＬスペクトル図である。FIG. 6 is an EL spectrum diagram.
【図７】この発明の素子の受光素子としての構成を示し
た断面図である。FIG. 7 is a cross-sectional view showing the configuration of the element of the present invention as a light receiving element.
【図８】図７の素子による分光感度の波長相関図である
。8 is a wavelength correlation diagram of spectral sensitivity of the element shown in FIG. 7; FIG.
【図９】多孔質シリコンのＸ線回折図である。FIG. 9 is an X-ray diffraction diagram of porous silicon.
１ シリコン単結晶基板 ２ 微小孔 ３ 多孔質シリコン（ＰＳ）層 1 Silicon single crystal substrate 2. Micropore 3 Porous silicon (PS) layer
Claims (14)
有する多孔質シリコンからなる発光多孔質シリコン。1. A light-emitting porous silicon made of porous silicon having micropores on the surface of a silicon single crystal substrate.
る発光素子。2. A light emitting device comprising the light emitting porous silicon according to claim 1.
。3. The light emitting device according to claim 2, which is an EL device.
有する多孔質シリコンからなる受発光多孔質シリコン。6. A light emitting/receiving porous silicon made of porous silicon having micropores on the surface of a silicon single crystal substrate.
なる受発光素子。7. A light emitting/receiving element made of the porous silicon according to claim 6.
ことを特徴とする請求項１または６の多孔質シリコンの
製造法。8. The method for producing porous silicon according to claim 1, wherein a silicon single crystal substrate is anodized.
次いで表面層をエッチング処理することを特徴とする請
求項１または６の多孔質シリコンの製造法。[Claim 9] Anodizing a silicon single crystal substrate,
7. The method for producing porous silicon according to claim 1, further comprising etching the surface layer.
多孔質シリコンの製造法。10. The method for producing porous silicon according to claim 9, wherein the porous silicon is subjected to chemical etching treatment.
電流を通電する請求項８または９の多孔質シリコンの製
造法。11. The method for producing porous silicon according to claim 8 or 9, wherein a short circuit current is applied while irradiating light in a chemical conversion bath.
板からなる多孔質シリコン。12. Porous silicon consisting of a silicon single crystal plate having micropores through it.
は受発光素子。13. A light-emitting, light-receiving, or light-receiving/emitting element according to claim 12.
通電電流を電解研磨の水準に増大し、生成した多孔質シ
リコン層のみを単離することを特徴とする請求項１２の
多孔質シリコン。14. The porous silicon according to claim 12, wherein in anodizing the silicon single crystal, the applied current is increased to the level of electrolytic polishing, and only the generated porous silicon layer is isolated.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP19866891A JP3306077B2 (en) | 1991-03-28 | 1991-07-13 | Porous silicon light-emitting device, porous silicon light-receiving device, and methods of manufacturing the same |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP6505491 | 1991-03-28 | ||
| JP3-65054 | 1991-03-28 | ||
| JP19866891A JP3306077B2 (en) | 1991-03-28 | 1991-07-13 | Porous silicon light-emitting device, porous silicon light-receiving device, and methods of manufacturing the same |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPH04356977A true JPH04356977A (en) | 1992-12-10 |
| JP3306077B2 JP3306077B2 (en) | 2002-07-24 |
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ID=26406197
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| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP19866891A Expired - Fee Related JP3306077B2 (en) | 1991-03-28 | 1991-07-13 | Porous silicon light-emitting device, porous silicon light-receiving device, and methods of manufacturing the same |
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| Country | Link |
|---|---|
| JP (1) | JP3306077B2 (en) |
Cited By (8)
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| WO1995002259A1 (en) * | 1993-07-07 | 1995-01-19 | Huth Gerald C | An optically interactive nanostructure |
| EP0893834A3 (en) * | 1993-11-02 | 1999-05-06 | Matsushita Electric Industrial Co., Ltd | Semiconductor device comprising an aggregate of semiconductor micro-needles |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| WO1995002259A1 (en) * | 1993-07-07 | 1995-01-19 | Huth Gerald C | An optically interactive nanostructure |
| US6734451B2 (en) | 1993-11-02 | 2004-05-11 | Matsushita Electric Industrial Co., Ltd. | Aggregate of semiconductor micro-needles and method of manufacturing the same, and semiconductor apparatus and method of manufacturing the same |
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| EP0887866A3 (en) * | 1993-11-02 | 1999-05-06 | Matsushita Electric Industrial Co., Ltd | Semiconductor device comprising an aggregate of semiconductor micro-needles |
| US6033928A (en) * | 1993-11-02 | 2000-03-07 | Matsushita Electric Industrial Co., Ltd. | Method of manufacturing aggregate of semiconductor micro-needles |
| US6087197A (en) * | 1993-11-02 | 2000-07-11 | Matsushita Electric Industrial Co., Ltd. | Aggregate of semiconductor micro-needles and method of manufacturing the same, and semiconductor apparatus and method of manufacturing the same |
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| EP0893834A3 (en) * | 1993-11-02 | 1999-05-06 | Matsushita Electric Industrial Co., Ltd | Semiconductor device comprising an aggregate of semiconductor micro-needles |
| US6943048B2 (en) | 2000-03-09 | 2005-09-13 | Matsushita Electric Industrial Co., Ltd. | Method for manufacturing optoelectronic material |
| WO2004064189A1 (en) * | 2003-01-14 | 2004-07-29 | Japan Science And Technology Agency | Light-detectable solid thin-film secondary battery |
| US7276312B2 (en) | 2003-01-14 | 2007-10-02 | Japan Science And Technology Agency | Light-detectable solid thin-film secondary battery |
| JP2005008909A (en) * | 2003-06-16 | 2005-01-13 | Canon Inc | Structure manufacturing method |
| WO2006051641A1 (en) * | 2004-11-15 | 2006-05-18 | National University Corporation Gunma University | Method for forming porous semiconductor film, light-emitting device and optical sensor |
| JP2008053446A (en) * | 2006-08-24 | 2008-03-06 | Hamamatsu Photonics Kk | Semiconductor element |
| US8110836B2 (en) | 2006-08-24 | 2012-02-07 | Hamamatsu Photonics K.K. | Semiconductor device |
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