JPH04187597A - Production of thin film of gallium nitride - Google Patents
Production of thin film of gallium nitrideInfo
- Publication number
- JPH04187597A JPH04187597A JP31872890A JP31872890A JPH04187597A JP H04187597 A JPH04187597 A JP H04187597A JP 31872890 A JP31872890 A JP 31872890A JP 31872890 A JP31872890 A JP 31872890A JP H04187597 A JPH04187597 A JP H04187597A
- Authority
- JP
- Japan
- Prior art keywords
- substrate
- thin film
- gallium nitride
- gas
- raw material
- 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.)
- Pending
Links
- 239000010409 thin film Substances 0.000 title claims abstract description 51
- 229910002601 GaN Inorganic materials 0.000 title claims abstract description 46
- JMASRVWKEDWRBT-UHFFFAOYSA-N Gallium nitride Chemical compound [Ga]#N JMASRVWKEDWRBT-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 238000004519 manufacturing process Methods 0.000 title claims description 21
- 239000000758 substrate Substances 0.000 claims abstract description 61
- 239000002994 raw material Substances 0.000 claims abstract description 21
- 238000010438 heat treatment Methods 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 11
- 229910052732 germanium Inorganic materials 0.000 claims description 7
- GYHNNYVSQQEPJS-UHFFFAOYSA-N Gallium Chemical compound [Ga] GYHNNYVSQQEPJS-UHFFFAOYSA-N 0.000 claims description 6
- 229910052733 gallium Inorganic materials 0.000 claims description 6
- 229910052725 zinc Inorganic materials 0.000 claims description 4
- 229910052793 cadmium Inorganic materials 0.000 claims description 3
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims description 3
- 229910052718 tin Inorganic materials 0.000 claims description 3
- 229910052711 selenium Inorganic materials 0.000 claims description 2
- 238000005121 nitriding Methods 0.000 claims 1
- 239000007789 gas Substances 0.000 abstract description 26
- 239000013078 crystal Substances 0.000 abstract description 8
- 230000001678 irradiating effect Effects 0.000 abstract description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 12
- 230000003287 optical effect Effects 0.000 description 7
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 6
- 239000010408 film Substances 0.000 description 5
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 5
- 238000007796 conventional method Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 3
- 238000010586 diagram Methods 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 230000002411 adverse Effects 0.000 description 2
- 238000000354 decomposition reaction Methods 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000003475 lamination Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- 229910052594 sapphire Inorganic materials 0.000 description 1
- 239000010980 sapphire Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- XCZXGTMEAKBVPV-UHFFFAOYSA-N trimethylgallium Chemical compound C[Ga](C)C XCZXGTMEAKBVPV-UHFFFAOYSA-N 0.000 description 1
- 238000000927 vapour-phase epitaxy Methods 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Abstract
Description
【発明の詳細な説明】
［産業上の利用分野コ
本発明は青色発光ダイオードや青色半導体レーザへの応
用か期待される窒化ガリウム薄膜の製造方法に関し、特
に均一で平坦性のよい窒化ガリウム薄膜を製造する方法
に関するものである。[Detailed Description of the Invention] [Industrial Field of Application] The present invention relates to a method for producing a gallium nitride thin film, which is expected to be applied to blue light emitting diodes and blue semiconductor lasers, and particularly relates to a method for producing a gallium nitride thin film that is uniform and has good flatness. It relates to a manufacturing method.
「従来の技術］
窒化ガリウム（Ｇ ａ Ｎ）は、約３．４ｅＶの塩エネ
ルギーギャップをもつ直接遷移型の化合物半導体で青色
から紫外領域にわたる発光素子として有望な材料である
。"Prior Art" Gallium nitride (G a N) is a direct transition type compound semiconductor with a salt energy gap of about 3.4 eV, and is a promising material as a light emitting element in the blue to ultraviolet region.
従来、ＧａＮ薄膜の製造法として有機金属気相成長（Ｍ
ＯＣＶＤ）法が知られている。これは、トリメチルガリ
ウム（Ｇ ａ （ＣＨ３） ３ ）とアンモニア（ＮＨ
３）を１０００℃程度に加熱した基板（通常、サファイ
ア（α−Ａ１２０３））表面上で分解、反応させ、Ｇａ
Ｎ薄膜を製造しようとするものである。Conventionally, metal organic vapor phase epitaxy (M
OCVD) method is known. This is trimethylgallium (G a (CH3) 3 ) and ammonia (NH
3) is decomposed and reacted on the surface of a substrate (usually sapphire (α-A1203)) heated to about 1000°C,
The purpose is to manufacture an N thin film.
［発明が解決しようとする課題］
しかし、ＧａＮとα−Ａ１２０３の格子定数の整合性は
悪く、また熱膨張係数の差も大きいため、製造したＧａ
Ｎ薄膜にはピットやクラックが入りやすく、均一で平坦
性のよいＧａＮ薄膜の製造が困難であった。[Problems to be solved by the invention] However, since the lattice constants of GaN and α-A1203 have poor matching, and the difference in thermal expansion coefficient is large, the produced Ga
N thin films are prone to pits and cracks, making it difficult to produce uniform and flat GaN thin films.
本発明は、前記課題を解決するため、加熱された基板表
面にガリウムを含む原料及び窒素を含む原料を供給して
窒化ガリウム薄膜を製造する方法において、特定の製造
条件を採用することにより、均一で平坦性のよい窒化ガ
リウム（Ｇ ａ Ｎ）薄膜の製造方法を提供することを
目的とする。In order to solve the above-mentioned problems, the present invention provides a method for manufacturing a gallium nitride thin film by supplying a gallium-containing raw material and a nitrogen-containing raw material to the surface of a heated substrate, by adopting specific manufacturing conditions. An object of the present invention is to provide a method for manufacturing a gallium nitride (GaN) thin film with good flatness.
［課題を解決するための手段］
前記目的を達成するため、本発明の窒化ガリウム薄膜の
製造方法は、加熱された基板表面にガリウムを含む原料
及び窒素を含む原料を供給して窒化ガリウム薄膜を製造
する方法において、前記基板の加熱温度を２段階に変化
させ、第１段階の基板温度を第２段階の基板温度より低
温にするとともに、少なくとも第１段階において前記基
板表面に光を照射させることを特徴とする。[Means for Solving the Problems] In order to achieve the above object, the method for producing a gallium nitride thin film of the present invention supplies a gallium-containing raw material and a nitrogen-containing raw material to a heated substrate surface to form a gallium nitride thin film. In the manufacturing method, the heating temperature of the substrate is changed in two stages, the substrate temperature in the first stage is lower than the substrate temperature in the second stage, and the surface of the substrate is irradiated with light in at least the first stage. It is characterized by
前記本発明の構成においては、第１段階における照射光
が、３６６ ｎｍ以下の波長を含む光であることが好ま
しい。In the configuration of the present invention, it is preferable that the irradiation light in the first stage is light containing a wavelength of 366 nm or less.
また、前記本発明の構成においては、第１段階の基板温
度を、５００℃〜７５０°Ｃの範囲に設定することが好
ましい。Further, in the configuration of the present invention, it is preferable that the substrate temperature in the first stage is set in a range of 500°C to 750°C.
また、前記本発明の構成においては、第２段階の基板温
度を、９００℃〜１１０００Ｃの範囲に設、定すること
か好ましい。Further, in the configuration of the present invention, it is preferable that the substrate temperature in the second stage is set within a range of 900°C to 11000°C.
また、前記本発明の構成においては、第２段階の窒化ガ
リウム薄膜成長中に、Ｓｅ、 Ｓｉ、 Ｇｅ。Furthermore, in the configuration of the present invention, Se, Si, and Ge are added during the second stage of growing the gallium nitride thin film.
Ｓｎから選ばれる少なくとも１種類を含む原料を基板表
面に供給することが好ましい。It is preferable to supply a raw material containing at least one type selected from Sn to the substrate surface.
また、前記本発明の構成においては、第２段階の窒化ガ
リウム薄膜成長中に、Ｃｄ、 Ｇｅ、 Ｂｅ。Furthermore, in the configuration of the present invention, Cd, Ge, and Be are added during the second stage of growing the gallium nitride thin film.
Ｍｇ、Ｚｎ、Ｌｉから選ばれる少なくとも１種類を含む
原料を基板表面に供給することが好ましい。It is preferable to supply a raw material containing at least one selected from Mg, Zn, and Li to the surface of the substrate.
［作用］
前記本発明方法の構成によれば、基板の加熱温度を２段
階に変化させ、第１段階の基板温度を第２段階の基板温
度より低温にして積層するので、これによって得られる
積層構造のＧａＮ薄膜は、基板の影響を受けに＜＜、表
面モフォロジーおよび結晶性が良好で、優れた電気的光
学的特性を示す薄膜とすることができる。また、少なく
とも第１段階において前記基板表面に光を照射させるの
で、光を照射して形成されたＧａＮ薄膜はその後の真空
中での加熱においても非常に安定で鏡面を維持すること
ができる。[Function] According to the configuration of the method of the present invention, the heating temperature of the substrate is changed in two stages, and the lamination is performed with the substrate temperature in the first stage being lower than the substrate temperature in the second stage, so that the laminated layer obtained thereby The GaN thin film of this structure has good surface morphology and crystallinity under the influence of the substrate, and can be made into a thin film that exhibits excellent electrical and optical properties. Furthermore, since the substrate surface is irradiated with light in at least the first step, the GaN thin film formed by irradiation with light is very stable and can maintain its mirror surface even during subsequent heating in vacuum.
また、第１段階における照射光が、３６６ ｎｍ以下の
波長を含む光であるという本発明の好ましい構成によれ
ば、成長中のＧａＮ薄膜に吸収され、原料の分解、反応
を促進して低温においても結晶性の良好なＧａＮ薄膜が
形成できる。Furthermore, according to a preferred configuration of the present invention in which the irradiation light in the first stage is light containing a wavelength of 366 nm or less, it is absorbed by the growing GaN thin film, promotes the decomposition and reaction of the raw material, and is heated at low temperatures. Also, a GaN thin film with good crystallinity can be formed.
また、第１段階の基板温度を、５００℃〜７５０°Ｃの
範囲に設定するという本発明の構成によれば、得られる
膜の結晶性および平坦性を良好なものとすることができ
る。Further, according to the configuration of the present invention in which the substrate temperature in the first stage is set in the range of 500° C. to 750° C., the obtained film can have good crystallinity and flatness.
また、第２段階の基板温度を、９００℃〜１１００°Ｃ
の範囲に設定するという本発明の構成によれば、得られ
る膜の電気的光学特性を良好なものとすることができ、
空孔も少なく不純物ドーピングに悪影響を与えることも
少ない。In addition, the substrate temperature in the second stage was set to 900°C to 1100°C.
According to the configuration of the present invention in which the temperature is set within the range of , the obtained film can have good electrical and optical properties,
There are few vacancies, and there is little adverse effect on impurity doping.
また、第２段階の窒化ガリウム薄膜成長中に、Ｓｅ、Ｓ
ｉ、Ｇｅ、Ｓｎから選ばれる少なくとも１種類を含む原
料を基板表面に供給するという本発明の構成によれば、
ｎ型伝導のＧａＮ薄膜（キャリヤ密度１０１８以上）を
得ることができる。Also, during the second stage of gallium nitride thin film growth, Se, S
According to the configuration of the present invention in which a raw material containing at least one selected from i, Ge, and Sn is supplied to the substrate surface,
A GaN thin film with n-type conductivity (carrier density of 1018 or more) can be obtained.
また、第２段階の窒化ガリウム薄膜成長中に、Ｃｄ、Ｇ
ｅ、Ｂｅ、Ｍｇ、Ｚｎ、Ｌｉから選ばれる少なくとも１
種類を含む原料を基板表面に供給するという本発明の好
ましい構成によれば、ｐ型伝導のＧａＮ薄膜（キャリヤ
密度１０１８以上）を得ることかできる。Also, during the second stage of gallium nitride thin film growth, Cd, G
At least one selected from e, Be, Mg, Zn, and Li
According to the preferred configuration of the present invention, in which a raw material containing various types of materials is supplied to the substrate surface, it is possible to obtain a p-type conductive GaN thin film (carrier density of 10 18 or more).
［実施例］ 以下、本発明を実施例により詳細に説明する。[Example] Hereinafter, the present invention will be explained in detail with reference to Examples.
本実施例では、ＧａＮ薄膜を製造する場合、まず、従来
の方法より低い温度（例えば５００℃〜７５０℃）に加
熱された基板表面にガリウム原料及び窒素原料を同時に
供給しつつ、基板表面に光（例えばキセノン（Ｘｅ）ラ
ンプ光）を照射してＧａＮ薄膜を形成する。この光を照
射して形成されたＧａＮ薄膜は従来法に比べてかなり低
温で形成されたにもかかわらず結晶性に優れかつ鏡面の
表面モフォロジーを示した。さらには、光を照射しない
で同じ温度で形成されたＧａＮ薄膜がその後の真空中で
の加熱（１０００℃程度）によって基板から剥がれるの
に対し、光を照射して形成されたＧａＮ薄膜はその後の
真空中での加熱においても非常に安定で鏡面を維持する
ことを本発明者らは確認した。In this example, when manufacturing a GaN thin film, first, a gallium raw material and a nitrogen raw material are simultaneously supplied to a substrate surface heated to a temperature lower than that in the conventional method (for example, 500°C to 750°C), and light is applied to the substrate surface. (For example, xenon (Xe) lamp light) is irradiated to form a GaN thin film. The GaN thin film formed by irradiation with this light had excellent crystallinity and a mirror surface morphology, even though it was formed at a much lower temperature than in conventional methods. Furthermore, while a GaN thin film formed at the same temperature without irradiation with light peels off from the substrate by subsequent heating in vacuum (approximately 1000°C), a GaN thin film formed with light irradiation peels off from the substrate afterward. The present inventors have confirmed that the material is extremely stable and maintains a mirror surface even when heated in a vacuum.
しかしながら、この光を照射しつつ低温で形成されたＧ
ａＮ薄膜のままでは従来法に比べ電気的光学的特性が劣
るため、本発明者らは、光を照射して低温で形成された
ＧａＮ薄膜の上に従来法と同程度の温度（例えば９００
℃〜１１００６Ｃ）でＧａＮ薄膜を積層することを試み
た。However, while irradiating this light, G formed at low temperature
Since the electro-optical properties of an aN thin film are inferior to those of conventional methods, the present inventors applied heat treatment to a GaN thin film formed at a low temperature by irradiation with light at a temperature similar to that of the conventional method (for example, 900°C).
An attempt was made to deposit GaN thin films at a temperature of 11,006°C.
その結果、この積層構造のＧａ・Ｎ薄膜は基板の影響を
受けることなく表面モフオロジー、結晶性か非常に良好
で、優れた電気的光学的特性を示すことを本発明者らは
確認した。As a result, the present inventors confirmed that the Ga/N thin film with this laminated structure has very good surface morphology and crystallinity without being affected by the substrate, and exhibits excellent electrical and optical properties.
第１図は本発明の製造方法の一実施例で用いられるＭＯ
ＣＶＤ装置の構造を示す概略図である。FIG. 1 shows an MO used in an embodiment of the manufacturing method of the present invention.
1 is a schematic diagram showing the structure of a CVD apparatus.
同図において、１は真空容器、２は真空ポンプ、３は基
板、４は基板ホルダ、５はヒータ、６ａはＧａ’（ＣＨ
３） ３ガス、６ｂはＮＨ３ガス、６ＣはＨ２ガス、７
ａ、ｂ、ｃはマスフローコントローラ、８ａ、ｂ、ｃは
ノズル、９はＸｅランプ、ｌＱａ、ｂ、Ｃ，はＸｅラン
プ光、１１はコリメータ、１２はハーフミラ−１１３は
パワーメータ、１４は窓である。In the figure, 1 is a vacuum container, 2 is a vacuum pump, 3 is a substrate, 4 is a substrate holder, 5 is a heater, and 6a is Ga' (CH
3) 3 gas, 6b is NH3 gas, 6C is H2 gas, 7
a, b, c are mass flow controllers, 8a, b, c are nozzles, 9 is a Xe lamp, lQa, b, C, are Xe lamp lights, 11 is a collimator, 12 is a half mirror, 113 is a power meter, 14 is a window be.
実際の薄膜成長は次のような手順で行なう。まず表面を
清浄にした基板３を基板ホルダ４に装着する。この場合
基板３は例えばα−ＡＩ２０３とする。次に真空容器１
を真空ポンプ２により例えば１０’Ｔｏｒｒ以下程度の
高真空まで排気する。Actual thin film growth is performed in the following steps. First, the substrate 3 whose surface has been cleaned is mounted on the substrate holder 4. In this case, the substrate 3 is made of α-AI203, for example. Next, vacuum container 1
is evacuated by the vacuum pump 2 to a high vacuum of, for example, 10' Torr or less.
次に基板３をヒータ５により第１の結晶成長に適切な温
度にする。この場合には例えば７００°Ｃとする。次に
Ｘｅランプ９を点灯する。Ｘｅランプ光１０ａはコリメ
ータ１１により平行光にされ、その後、ハーフミラ−１
２により同強度の二つの光１０ｂ、１０ｃとなり、光１
０ｂは窓１４を通って基板３に照射される。光１０ｃの
強度をパワーメータ１３により測定することにより、基
板３に照射される光１０ｂの強度を知る。光１０ｂの強
度をＸｅランプ９を調節することにより、第１の結晶成
長に必要な強度にする。この場合例えは５００ｍＷ／ａ
ｌとする。次にＧａ （ＣＨ３）３カス６ａ及びＮＨ３
カス６ｂの流量をマスフローコントローラ７ａ、ｂによ
り適当な流量比になるよう調節し、ノズル８ａ、ｂによ
り基板３表面に供給する。また、同時にノズル８ｃより
Ｈ２ガス６Ｃを真空容器１内に導入する。この場合の流
量は、例えばＧ ａ （ＣＨ３） ３ガス６ａが０．３
ｓｅｃｍ、ＮＨガス６ｂが２７０ｓｅｃｍ、Ｈ２ガス６
ｃが５０ｓｅｃｍとする。用いたＸｅランプ光は第２図
に示すようにＧａＮのバンドギャップに相当する波長（
室温で３６６ｎｍ）以下の波長の光を含んでいるため、
成長中のＧａＮ薄膜に吸収され、原料の分解、反応を促
進して低温においても結晶性の良好なＧａＮ薄膜が形成
できる。Next, the substrate 3 is brought to a temperature suitable for the first crystal growth using the heater 5. In this case, the temperature is set to 700°C, for example. Next, the Xe lamp 9 is turned on. The Xe lamp light 10a is made into parallel light by a collimator 11, and then a half mirror 1
2 results in two lights 10b and 10c with the same intensity, and light 1
0b is irradiated onto the substrate 3 through the window 14. By measuring the intensity of the light 10c with the power meter 13, the intensity of the light 10b irradiated onto the substrate 3 is known. By adjusting the intensity of the light 10b using the Xe lamp 9, the intensity required for the first crystal growth is made. In this case, the example is 500mW/a
Let it be l. Next, Ga (CH3)3 residue 6a and NH3
The flow rate of the waste 6b is adjusted to an appropriate flow rate ratio by mass flow controllers 7a, b, and is supplied to the surface of the substrate 3 through nozzles 8a, b. At the same time, H2 gas 6C is introduced into the vacuum container 1 from the nozzle 8c. In this case, the flow rate is, for example, 0.3 for Ga (CH3) 3 gas 6a.
secm, NH gas 6b is 270sec, H2 gas 6
Assume that c is 50 seconds. The Xe lamp light used has a wavelength corresponding to the bandgap of GaN (as shown in Figure 2).
Because it contains light with a wavelength of 366 nm or less at room temperature,
It is absorbed into the growing GaN thin film, accelerates the decomposition and reaction of the raw material, and allows the formation of a GaN thin film with good crystallinity even at low temperatures.
ここで、原料ガスの供給をいったん中止し、真空容器１
を真空ポンプ２により例えば１０ ’Ｔ 。At this point, the supply of raw material gas is temporarily stopped, and the
for example 10'T by vacuum pump 2.
ｒｒ以下程度の高真空まで排気する。次に基板３をヒー
タ５により第２の結晶成長に適切な温度にする。この場
合には例えば１００００Ｃとする。次にＧａ （ＣＨ３
）３ガス６ａ及びＮＨ３ガス６ｂの流量をマスフローコ
ントローラ７ａ、ｂｌ：より適当な流量比になるよう調
節し、ノズル８ａ、ｂにより基板３表面に供給する。ま
た、同時にノズル８ＣよりＨ２ガス６ｃを真空容器１内
に導入する。この場合の流量は、例えばＧ ａ （ＣＨ
３） ３ガス６ａが０．３ ｓ ｃ ｃｍＸＮＨ３ガス
６ｂが２７０ｓｃｃｍ、Ｈ２ガス６Ｃが５０ｓ＋ｃｃｍ
とする。この場合、Ｘｅランプ９は点灯してもしなくて
もよい。このように第１のＧａＮ薄膜の上に第２のＧａ
Ｎ薄膜を積層させて結晶成長を行なった。Evacuate to a high vacuum of about rr or less. Next, the substrate 3 is brought to a temperature suitable for second crystal growth using the heater 5. In this case, it is set to 10000C, for example. Next, Ga (CH3
) The flow rates of the NH3 gas 6a and the NH3 gas 6b are adjusted to a more appropriate flow rate ratio between the mass flow controllers 7a and bl, and are supplied to the surface of the substrate 3 through the nozzles 8a and 8b. At the same time, H2 gas 6c is introduced into the vacuum container 1 from the nozzle 8C. The flow rate in this case is, for example, G a (CH
3) 3 gas 6a is 0.3 s c cmX NH3 gas 6b is 270 sccm, H2 gas 6C is 50 s + ccm
shall be. In this case, the Xe lamp 9 may or may not be lit. In this way, the second GaN film is placed on top of the first GaN thin film.
Crystal growth was performed by stacking N thin films.
以上のような方法で製造したＧａＮ薄膜は、均一で平坦
性がよく、また優れた電気的光学的特性を示した。また
、第２の結晶成長中にＣｄ、Ｇｅ。The GaN thin film produced by the method described above was uniform and had good flatness, and exhibited excellent electrical and optical properties. In addition, Cd and Ge are added during the second crystal growth.
Ｂｅ、Ｍｇ、Ｚｎ、Ｌｉの内の１種類を含む原料気体分
子を基板表面に供給することによって、ｎ型伝導のＧａ
Ｎ薄膜（キャリヤ密度１０１８以上）が製造できること
を、また、ＧａＮ薄膜製造中にＳｅ、Ｓｉ、Ｇｅ、Ｓｎ
の内の１種類を含む原料気体分子を基板表面に供給する
ことによって、ｎ型伝導のＧａＮ薄膜（キャリヤ密度１
０１８以上）が製造できることを確認した。By supplying raw material gas molecules containing one of Be, Mg, Zn, and Li to the substrate surface, n-type conduction Ga
It was also confirmed that N thin films (carrier density of 1018 or more) can be produced, and that Se, Si, Ge, Sn, etc.
By supplying raw material gas molecules containing one type of
018 or higher) was confirmed to be able to be manufactured.
なお上述の実施例では、Ｈ２ガス６Ｃを用いたが、必ず
しも必要ではないが、Ｈ２は反応の促進とＧａＮ薄膜へ
中の炭素原子の混入を防ぐ効果かある。また、原料ガス
は上述の実施例に限らず、ガリウム、窒素を含むもので
あればよい。Although H2 gas 6C was used in the above embodiment, H2 has the effect of accelerating the reaction and preventing the inclusion of carbon atoms into the GaN thin film, although this is not necessarily necessary. Further, the raw material gas is not limited to the above-mentioned embodiments, and may be any gas containing gallium and nitrogen.
また、上述の実施例では基板としてα−ＡＩ。Further, in the above embodiment, α-AI is used as the substrate.
０３を用いたがＧａＡｓ、Ｓｉ、ＳｉＣ等他の基板を用
いてもよい。Although 03 was used, other substrates such as GaAs, Si, and SiC may also be used.
さらに、光源はＸｅランプに限らず、ＧａＮのバンドギ
ャップに相当する波長以下の光を含むものであれば同様
の効果が得られる。Furthermore, the light source is not limited to a Xe lamp, and the same effect can be obtained as long as it contains light with a wavelength equal to or less than the bandgap of GaN.
また、第１の結晶成長の基板温度は、５００℃以上７５
０℃以下が好適である。５００℃以下では膜の結晶性が
悪化する傾向となり、また７５０℃以上では平坦性が悪
化するする傾向となる。Further, the substrate temperature for the first crystal growth is 500°C or higher and 75°C.
The temperature is preferably 0°C or lower. At temperatures below 500° C., the crystallinity of the film tends to deteriorate, and at temperatures above 750° C., the flatness tends to deteriorate.
また、第２の結晶成長の基板温度は、９００°Ｃ以上１
１００’Ｃが好適である。９００℃以下では電気的光学
的特性が悪化する傾向となり、１１００℃以上では膜中
の窒素の空孔が多くなり不純物ドーピングに悪影響を及
ぼす傾向となる。Further, the substrate temperature for the second crystal growth is 900°C or higher.
100'C is preferred. Below 900°C, the electrical and optical properties tend to deteriorate, and above 1100°C, the number of nitrogen vacancies in the film increases, which tends to adversely affect impurity doping.
［発明の効果］
以上説明したように、本発明によれば、均一で平坦性の
よい、電気的光学的特性の優れたＧａＮ薄膜を製造する
ことかでき、青色発光ダイオードや青色半導体レーザ製
造に極めて有用である。[Effects of the Invention] As explained above, according to the present invention, it is possible to manufacture a GaN thin film that is uniform, has good flatness, and has excellent electrical and optical properties, and is suitable for manufacturing blue light emitting diodes and blue semiconductor lasers. Extremely useful.
第１図は本発明の一実施例で用いられる光Ｃ■Ｄ装置の
構造を示す概略図、第２図は本発明の一実施例で用いら
れるＸｅランプの分光分布図である。
１・・・真空容器、 ２・・・真空ポンプ、 ３・・・
基板、４・・・基板ホルダ、 ５・・・ヒータ、
６ａ・・・Ｇａ（ＣＨ） ガス、 ６ｂ・・・ＮＨ
３ガス、７Ｂ、ｂ、ｃ・・・マスフローコントローラ、
３ａ、ｂ、ｃ・・・ノズル、 ９・・・Ｘｅランプ、
ｌＱａ、ｂ、ｃ・・・Ｘｅランプ光、 １１ ・・・コ
リメータ、 １２・・・ハーフミラ−１１３・・・パ
ワーメータ、 １４・・・窓。FIG. 1 is a schematic diagram showing the structure of an optical CD device used in one embodiment of the present invention, and FIG. 2 is a spectral distribution diagram of a Xe lamp used in one embodiment of the present invention. 1... Vacuum container, 2... Vacuum pump, 3...
Substrate, 4... Substrate holder, 5... Heater,
6a...Ga(CH) gas, 6b...NH
3 gases, 7B, b, c...mass flow controller,
3a, b, c... nozzle, 9... Xe lamp,
lQa, b, c...Xe lamp light, 11...collimator, 12...half mirror 113...power meter, 14...window.
Claims (1)
素を含む原料を供給して窒化ガリウム薄膜を製造する方
法において、前記基板の加熱温度を２段階に変化させ、
第１段階の基板温度を第２段階の基板温度より低温にす
るとともに、少なくとも第１段階において前記基板表面
に光を照射させることを特徴とする窒化ガリウム薄膜の
製造方法。（２）第１段階における照射光が、３６６ｎ
ｍ以下の波長を含む光である特許請求の範囲第１項記載
の窒化ガリウム薄膜の製造方法。 （３）第１段階の基板温度を、５００℃〜７５０℃の範
囲に設定した請求項１記載の窒化ガリウム薄膜の製造方
法。 （４）第２段階の基板温度を、９００℃〜１１００℃の
範囲に設定した請求項１記載の窒化ガリウム薄膜の製造
方法。 （５）第２段階の窒化ガリウム薄膜成長中に、Ｓｅ、Ｓ
ｉ、Ｇｅ、Ｓｎから選ばれる少なくとも１種類を含む原
料を基板表面に供給する請求項１または４記載の窒化ガ
リウム薄膜の製造方法。（６）第２段階の窒化ガリウム
薄膜成長中に、Ｃｄ、Ｇｅ、Ｂｅ、Ｍｇ、Ｚｎ、Ｌｉか
ら選ばれる少なくとも１種類を含む原料を基板表面に供
給する請求項１、４または５記載の窒化ガリウム薄膜の
製造方法。Scope of Claims: (1) A method for manufacturing a gallium nitride thin film by supplying a gallium-containing raw material and a nitrogen-containing raw material to the heated substrate surface, the heating temperature of the substrate being changed in two stages,
A method for manufacturing a gallium nitride thin film, characterized in that the substrate temperature in the first step is lower than the substrate temperature in the second step, and the surface of the substrate is irradiated with light in at least the first step. (2) The irradiation light in the first stage is 366n
2. The method for producing a gallium nitride thin film according to claim 1, wherein the light includes a wavelength of m or less. (3) The method for manufacturing a gallium nitride thin film according to claim 1, wherein the substrate temperature in the first step is set in a range of 500°C to 750°C. (4) The method for manufacturing a gallium nitride thin film according to claim 1, wherein the substrate temperature in the second stage is set in a range of 900°C to 1100°C. (5) During the second stage of gallium nitride thin film growth, Se, S
5. The method for producing a gallium nitride thin film according to claim 1, wherein a raw material containing at least one selected from i, Ge, and Sn is supplied to the substrate surface. (6) The nitriding method according to claim 1, 4 or 5, wherein a raw material containing at least one selected from Cd, Ge, Be, Mg, Zn, and Li is supplied to the substrate surface during the second step of growing the gallium nitride thin film. Method for manufacturing gallium thin film.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31872890A JPH04187597A (en) | 1990-11-22 | 1990-11-22 | Production of thin film of gallium nitride |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP31872890A JPH04187597A (en) | 1990-11-22 | 1990-11-22 | Production of thin film of gallium nitride |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| JPH04187597A true JPH04187597A (en) | 1992-07-06 |
Family
ID=18102295
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP31872890A Pending JPH04187597A (en) | 1990-11-22 | 1990-11-22 | Production of thin film of gallium nitride |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH04187597A (en) |
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5496766A (en) * | 1994-03-28 | 1996-03-05 | Pioneer Electronic Corporation | Method for producing a luminous element of III-group nitride |
| JPH0878728A (en) * | 1994-08-22 | 1996-03-22 | Korea Res Inst Of Chem Technol | Growth of heteroepitaxial blue light-emitting gallium nitride |
| WO1997008356A3 (en) * | 1995-08-18 | 1997-04-24 | Steven P Denbaars | Modified metalorganic chemical vapor deposition of group III-V thin layers |
| US7473316B1 (en) * | 2000-04-12 | 2009-01-06 | Aixtron Ag | Method of growing nitrogenous semiconductor crystal materials |
-
1990
- 1990-11-22 JP JP31872890A patent/JPH04187597A/en active Pending
Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5496766A (en) * | 1994-03-28 | 1996-03-05 | Pioneer Electronic Corporation | Method for producing a luminous element of III-group nitride |
| JPH0878728A (en) * | 1994-08-22 | 1996-03-22 | Korea Res Inst Of Chem Technol | Growth of heteroepitaxial blue light-emitting gallium nitride |
| WO1997008356A3 (en) * | 1995-08-18 | 1997-04-24 | Steven P Denbaars | Modified metalorganic chemical vapor deposition of group III-V thin layers |
| US7473316B1 (en) * | 2000-04-12 | 2009-01-06 | Aixtron Ag | Method of growing nitrogenous semiconductor crystal materials |
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