KR100314843B1 - Method for forming photoluminescence layer of silicon photoluminescence device - Google Patents

Method for forming photoluminescence layer of silicon photoluminescence device Download PDF

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KR100314843B1
KR100314843B1 KR1019970038752A KR19970038752A KR100314843B1 KR 100314843 B1 KR100314843 B1 KR 100314843B1 KR 1019970038752 A KR1019970038752 A KR 1019970038752A KR 19970038752 A KR19970038752 A KR 19970038752A KR 100314843 B1 KR100314843 B1 KR 100314843B1
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silicon
light emitting
oxide film
forming
ions
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KR1019970038752A
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KR19990016267A (en
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김광일
고재석
이광철
정욱진
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이구택
포항종합제철 주식회사
신현준
재단법인 포항산업과학연구원
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/26—Materials of the light emitting region
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/005—Processes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L33/00—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L33/02—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies
    • H01L33/16—Semiconductor devices with at least one potential-jump barrier or surface barrier specially adapted for light emission; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by the semiconductor bodies with a particular crystal structure or orientation, e.g. polycrystalline, amorphous or porous
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L2933/00—Details relating to devices covered by the group H01L33/00 but not provided for in its subgroups
    • H01L2933/0008—Processes
    • H01L2933/0033—Processes relating to semiconductor body packages
    • H01L2933/0058—Processes relating to semiconductor body packages relating to optical field-shaping elements

Abstract

PURPOSE: A method for forming a photoluminescence layer is provided to produce a silicon photoluminescence device which emits intense red light. CONSTITUTION: A silicon oxide layer(2) is formed on a silicon substrate(1). Silicon ions are implanted into the silicon oxide layer(2) to produce an excessive point bond(4). A heat treatment is performed under nitrogen gas to form a super fine silicon crystal(5) within the silicon oxide layer(2) by joining operation of the silicon atoms with the excessive point bond. The silicon ions are implanted at the dose of less than 1x10 17/cm2. The heat is applied for more than 12 hours in an electric arc furnace.

Description

실리콘 발광 소자용 발광층 형성방법Method of forming light emitting layer for silicon light emitting device

본 발명은 발광소자 제조에 있어서 실리콘 기판을 이용하여 발광층을 형성하는 방법에 관한 것으로, 특히 실리콘 산화막 내부에 실리콘 점결함을 과잉 발생시키고 열처리에 의해 이들 점결함과 실리콘 원자들이 결합하여서 극미세 결정립층이 형성되도록 함으로써, 강한 적색 발광특성을 얻을 수 있는 실리콘 발광소자용 발광층 형성방법에 관한 것이다.BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method of forming a light emitting layer using a silicon substrate in the manufacture of a light emitting device. In particular, an excessive occurrence of silicon defects in a silicon oxide film is formed, and an extremely fine grain layer is formed by combining these defects and silicon atoms by heat treatment. The present invention relates to a method of forming a light emitting layer for a silicon light emitting device, by which a strong red light emitting property can be obtained.

최근 반도체 공정을 이용하여 광소자를 제작하는 연구가 계속되고 있으나, Ⅲ-Ⅴ족 반도체 기판과 양자우물구조 등의 정교한 결정질 반도체 초박막 성장기술이 요구되고 저온공정이 필요하는 등 많은 문제점을 가지고 있다. 그리고 다공질 실리콘을 이용하여 적색발광 등의 연구가 행해지고 있으나 다공질 실리콘의 제작은 화학적 에칭법을 사용하므로 재현성과 발광되는 빛의 안정성에 문제가 되고 있다.Recently, research into fabricating an optical device using a semiconductor process has been continued, but there are many problems such as requiring a crystalline semiconductor ultra thin film growth technology such as a III-V semiconductor substrate and a quantum well structure and a low temperature process. In addition, research on red light emission and the like has been conducted using porous silicon, but the production of porous silicon has a problem in reproducibility and stability of light emitted due to the use of a chemical etching method.

그러므로 안정성있는 발광특성, 기계적 강도, 재현성 있는 제작 등을 고려하여 실리카나 산화막에 극미세 결정립을 제작하여 발광특성을 얻고자 하는 노력이 계속되고 있다. 그러나 이러한 방법의 경우 여러 피크가 검출되거나 (Appl. Phys. Lett, 65(14), 3, 1994, 1814) 완만한 피크가 검출되어서(J, Phys, : Condens, Matter 5(1993) L375-L380) 미미한 적색광이 검출되어서, 강한 적색광을 얻기에는 어려움이 많은 문제점이 있다.Therefore, in consideration of stable light emission characteristics, mechanical strength, and reproducible production, efforts have been made to obtain light emission characteristics by fabricating ultrafine grains in silica or oxide films. However, for these methods, several peaks are detected (Appl. Phys. Lett, 65 (14), 3, 1994, 1814) or gentle peaks are detected (J, Phys .: Condens, Matter 5 (1993) L375-L380 A slight red light is detected, which makes it difficult to obtain strong red light.

본 발명은 상기한 문제점을 해결하고 개선점을 달성하기 위해 안출한 것이다. 따라서, 본 발명의 목적은 강한 적색광을 발광할 수 있는 실리콘 발광소자용 발광층 형성방법을 제공하는데 있다.The present invention has been made to solve the above problems and to achieve an improvement. Accordingly, an object of the present invention is to provide a method of forming a light emitting layer for a silicon light emitting device capable of emitting strong red light.

도 1a 내지 도 1c는 본 발명에 의한 발광층 형성방법을 실시하기 위한 공정의 일예를 단계적으로 나타내는 모식도이다.1A to 1C are schematic diagrams showing one example of a step for performing a light emitting layer forming method according to the present invention.

도 2는 본 발명에 의한 발광층 형성방법으로 실리콘 산화막에 실리콘 이온을 주입하여 열처리 하였을 때의 발광(PL:photoluminescence) 특성곡선이다.FIG. 2 is a light emission characteristic curve of the light emitting layer formed by heat treatment by injecting silicon ions into the silicon oxide film.

도 3는 도 2와 비교를 위하여 실리콘 산화막에 실리콘 이온을 고 도우즈(dose)로 주입하여 열처리 하였을 때의 발광 특성곡선이다.FIG. 3 is a light emission characteristic curve when silicon ions are injected into a silicon oxide film with a high dose and heat treated for comparison with FIG. 2.

* 도면의 주요 부분에 대한 부호의 설명 *Explanation of symbols on the main parts of the drawings

1 ..... 실리콘 기판 2 ..... 실리콘 산화막1 ..... Silicon Substrate 2 ..... Silicon Oxide

3 ..... 실리콘 이온 4 ..... 실리콘 이온주입에 의한 점결함3 ..... Silicon ions 4 ..... Point defects due to silicon ion implantation

5 ..... 열처리에 의해 형성된 극미세 실리콘 결정립5 ..... Ultrafine Silicon Grain Formed by Heat Treatment

상기한 기술적인 과제를 달성하기 위한 기술적인 수단으로써, 본 발명에 의한 실리콘 발광소자용 발광층 형성방법은 실리콘 기판에 실리콘 산화막을 형성하는 제1단계와, 상기 제1단계의 산화막 내부에 점결함을 과잉 발생시키기 위하여 실리콘 이온을 이온주입하는 제2단계와, 상기 제2단계의 점결함과 실리콘 원자들이 결합하여 산화막 내부에 극미세 실리콘 결정립을 형성하여 강한 적색 발광을 유기시키도록 하기 위하여 질소분위기하에서 열처리하는 제3단계를 포함하여 이루어져, 강한 적색광을 발광시킬 수 있다.As a technical means for achieving the above technical problem, the method for forming a light emitting layer for a silicon light emitting device according to the present invention is excessive in the first step of forming a silicon oxide film on the silicon substrate and the interior of the oxide film of the first step The second step of ion implantation of silicon ions to generate, and the heat defects under nitrogen atmosphere to combine the defects of the second step and the silicon atoms to form ultra-fine silicon crystal grains in the oxide film to induce strong red light emission Including the third step, it can emit strong red light.

이하, 본 발명에 의한 실리콘 발광소자용 발광층 형성방법을 수행하기 위한 방법의 구성을 첨부도면 도 1을 참고로 설명한다.Hereinafter, the configuration of a method for performing a light emitting layer forming method for a silicon light emitting device according to the present invention will be described with reference to the accompanying drawings.

도 1a 내지 도 1c는 본 발명에 의한 실리콘 발광소자용 발광층 형성방법을 실시하기 위한 공정의 일예를 단계적으로 나타내는 모식도이다.1A to 1C are schematic diagrams showing an example of a step by step for carrying out the method for forming a light emitting layer for a silicon light emitting device according to the present invention.

본 발명에 의한 실리콘 발광소자용 발광층 형성방법은 실리콘 기판(1)에 실리콘 산화막(2)을 형성하는 제1단계와, 상기 제1단계의 산화막(2) 내부에 점결함(4)을 과잉 발생시키기 위하여 실리콘 이온(3)을 이온주입하는 제2단계와, 상기 제2단계의 점결함(4)과 실리콘 원자들이 결합하여 산화막(2) 내부에 극미세 실리콘 결정립(5)을 형성하여 강한 적색 발광을 유기시키도록 하기 위하여 질소분위기하에서 열처리하는 제3단계를 포함하여 구성된다.In the method of forming a light emitting layer for a silicon light emitting device according to the present invention, the first step of forming the silicon oxide film 2 on the silicon substrate 1 and the excessive generation of point defects 4 in the oxide film 2 of the first step are generated. The second step of ion implantation of silicon ions 3 and the point defects 4 of the second step and the silicon atoms are combined to form ultrafine silicon crystal grains 5 in the oxide film 2 to generate strong red light emission. And a third step of heat treatment under a nitrogen atmosphere to induce organic matter.

상기 제1단계의 산화막 형성은 습식 산화법을 사용할 수 있고, 상기 제2단계에서 주입되는 이온은 과잉 점결함 발생이 가능한 모든 이온이 가능하다. 상기 제2단계의 실리콘 이온주입량은 1 x 1017/cm2미만의 도우즈(dose)량에서 강한 적색 발광을 얻을 수 있으며 상기 제3단계의 열처리는 통상의 전기로 가열법을 사용할 수 있다. 상기 제3단계의 열처리는 12시간 이상 열처리를 수행하는 것이 효과적이다.The oxide film formation in the first step may use a wet oxidation method, and the ions implanted in the second step may be all ions capable of generating excessive point defects. The silicon ion implantation of the second step may obtain a strong red light emission at a dose of less than 1 x 10 17 / cm 2 and the heat treatment of the third step may use a conventional electric furnace heating method. The heat treatment of the third step is effective to perform the heat treatment for 12 hours or more.

이와같이 구성된 본 발명에 의한 실리콘 발광소자용 발광층 형성방법을 첨부도면 도 1에 의거하여 하기에 보다 상세히 설명한다.A light emitting layer forming method for a silicon light emitting device according to the present invention configured as described above will be described in more detail below with reference to FIG. 1.

도 1a 내지 도 1c는 본 발명에 의한 실리콘 발광소자용 발광층 형성방법을 실시하기 위한 공정의 일예를 단계적으로 나타내는 모식도이다.1A to 1C are schematic diagrams showing an example of a step by step for carrying out the method for forming a light emitting layer for a silicon light emitting device according to the present invention.

본 발명에 따라 강한 적색광을 얻기 위한 실리콘 발광소자용 발광층 형성을 위한 방법으로는, 우선, 도 1a에 나타난 바와같이, 실리콘 기판(1)에 통상의 방법으로 SiO2에 의한 산화막(2)을 형성한다. 다음에, 도 1b에 나타난 바와같이, 상기의 산화막에 Si 이온(3)을 사용하여 점결함(4)을 산화막내부에 과잉발생시키고, 다음에 도 1c에서와 같이 질소 분위기하에서 열처리를 통하면 실리콘 산화막 내부의 점결함과 이온주입된 실리콘 원자들이 상호 흡수 성장하여 극미세 실리콘 단결정상의 결정립층(5)이 형성된다.As a method for forming a light emitting layer for a silicon light emitting device for obtaining strong red light according to the present invention, first, as shown in FIG. 1A, an oxide film 2 made of SiO 2 is formed on a silicon substrate 1 by a conventional method. do. Next, as shown in FIG. 1B, the silicon oxide film is formed by excessively generating a point defect 4 in the oxide film by using Si ions 3 in the oxide film, and then heat treatment in a nitrogen atmosphere as shown in FIG. 1C. Internal point defects and ion implanted silicon atoms are mutually absorbed and grown to form a crystal grain layer 5 of ultrafine silicon single crystal phase.

도 1에서는 p 형 실리콘 기판을 사용하고, 그리고 불순물로서는 붕소(B)를 사용하였으나, 본 발명은 이에 한정되는 것은 아니다.Although a p-type silicon substrate is used in FIG. 1 and boron (B) is used as an impurity, the present invention is not limited thereto.

이하, 본 발명에 의한 실리콘 발광소자용 발광층 형성방법의 바람직한 실시예를 첨부한 도면 도 2 및 도 3을 참조하여 설명한다.Hereinafter, a preferred embodiment of a method of forming a light emitting layer for a silicon light emitting device according to the present invention will be described with reference to FIGS. 2 and 3.

도 2는 본 발명에 의한 방법으로 실리콘 산화막에 실리콘 이온을 주입하여 열처리 하였을 때의 발광(PL:photoluminescence) 특성곡선이고, 도 3는 도 2와 비교를 위하여 실리콘 산화막에 실리콘 이온을 고 도우즈(dose)로 주입하여 열처리 하였을 때의 발광 특성곡선이다.FIG. 2 is a luminescence (PL: photoluminescence) characteristic curve when the silicon oxide film is heat-treated by implanting silicon ions by the method according to the present invention, and FIG. 3 shows a high dose of silicon ions in the silicon oxide film for comparison with FIG. This is a light emission characteristic curve when injected at a dose) and heat treated.

실시예Example

p형(100) 방향이고 저항률이 7-15Ω㎝인 실리콘 기판에 SiO2산화막을 형성한 후, 상기 산화막에 가속전압 200KeV에서 도우즈량 5 × 1016/cm2과 1 × 1017/cm2으로 실리콘 이온을 임프란테이션(ion implantation)법으로 주입하였다.After a SiO 2 oxide film was formed on a silicon substrate having a p-type (100) direction and a resistivity of 7-15 μm cm, the oxide film had doses of 5 × 10 16 / cm 2 and 1 × 10 17 / cm 2 at an acceleration voltage of 200 KeV. Silicon ions were implanted by ion implantation.

이때 산화막 내부에 과잉 점결함들이 생성된다. 이온 주입이 끝난 시료는 통상의 열처리 방법에 의해 열처리를 함으로써 산화막 내부에 과잉 점결함들이 서로 흡수 성장하여서 극미세 결정립이 형성되어서 이들이 발광원으로 작용하게 된다.At this time, excess point defects are generated in the oxide film. After the ion implantation, the sample is heat-treated by a conventional heat treatment method, so that excess point defects are absorbed and grown in the oxide film to form ultra-fine grains, which act as a light emitting source.

도 2는 5 × 1016/cm2의 도우즈(dose)로 이온주입한 후, 1100℃ 에서 각각 30분에서 12시간 질소분위기에서 열처리한 시료의 발광(PL : photoluminescence)특성곡선을 나타낸다. 열처리 시간에 관계없이 적색발광 영역인 7400Å 에서 발광 피크가 관찰되며 열처리 시간이 증가함에 따라서 피크의 강도가 세어지고 12시간 정도에서 최대치를 나타낸다. 이는 산화막에 실리콘 이온이 주입될 때 과잉점결함이 생성되며 이들 점결함들이 열처리에 따라서 서로 흡수 성장해 감에 따라서 적색발광에 크게 기여하고 있음을 나타낸다.FIG. 2 shows the photoluminescence (PL) characteristic curve of samples subjected to ion implantation with a dose of 5 × 10 16 / cm 2 and then heat-treated in a nitrogen atmosphere at 1100 ° C. for 30 minutes to 12 hours. Irrespective of the heat treatment time, the luminescence peak was observed in the red light emitting region of 7400 Å. As the heat treatment time was increased, the intensity of the peak was increased and reached a maximum at about 12 hours. This indicates that excessive defects are generated when silicon ions are implanted into the oxide film, and these defects contribute significantly to red light emission as they absorb and grow with each other as a result of heat treatment.

도 3는 1 × 1017/cm2의 도우즈(dose)로 이온주입한 후, 1100℃ 에서 각각 30분에서 12시간 질소분위기에서 열처리한 시료의 발광(PL : photoluminescence) 특성곡선을 나타낸다. 열처리 시간에 관계없이 적색발광 영역인 7400Å 과 적외선 영역의 8500Å 에서 발광 피크가 혼재되어 관찰되며 열처리 시간이 증가함에 따라서 피크의 강도가 세어지고 12시간 정도에서 최대치를 나타낸다.FIG. 3 shows a photoluminescence characteristic curve of a sample subjected to ion implantation with a dose of 1 × 10 17 / cm 2 and then heat-treated in a nitrogen atmosphere at 1100 ° C. for 30 minutes to 12 hours. Irrespective of the heat treatment time, emission peaks are observed in the red light emitting region of 7400 Å and 8500 적외선 in the infrared region, and the intensity of the peak is increased as the heat treatment time increases and the maximum value is obtained at about 12 hours.

이로써 도우즈(dose)량이 1 × 1017/cm2미만인 경우에 강한 적색광을 얻을 수 있다는 결론을 얻을 수 있다.It can be concluded that strong red light can be obtained when the dose is less than 1 × 10 17 / cm 2 .

상술한 바와같은 본 발명에 따르면, 실리콘 산화막 내부에 실리콘 점결함을 과잉 발생시키고 열처리에 의해 이들 점결함과 실리콘 원자들이 결합하여서 극미세 결정립층이 형성되도록 함으로써, 강한 적색 발광특성을 얻을 수 있다.According to the present invention as described above, the strong red light emission characteristics can be obtained by excessively generating silicon defects in the silicon oxide film and by bonding the defects and silicon atoms by heat treatment to form an ultrafine grain layer.

이상의 설명은 단지 본 발명의 일실시예에 대한 설명에 불과하며, 본 발명은 그 구성과 기술적 사상의 범위내에서 다양한 변경 및 개조가 가능하다.The above description is only a description of one embodiment of the present invention, the present invention is capable of various changes and modifications within the scope of the configuration and technical spirit.

또한, 본 발명의 기술분야에서 통상의 지식을 가진자라면 상기 실리콘 발광소자용 발광층 형성방법이 상기 기술한 실시예에 한정되지 않고 실리콘 이온 대신에 과잉 점결함 발생이 가능한 모든 이온이 가능하고, 산화막 성장에서 습식산화법 대신에 모든 산화막 형성 방법이 가능하고, 열처리는 전기로 가열법을 포함한 모든 열처리 방법으로 대체가능함을 용이하게 알 수 있을 것이다.In addition, a person having ordinary knowledge in the technical field of the present invention is not limited to the above-described embodiment of the light emitting layer forming method for the silicon light emitting device, and all ions capable of generating excessive point defects instead of silicon ions are possible, and oxide film growth is possible. It will be readily understood that all oxide film formation methods are possible in place of the wet oxidation method, and that the heat treatment can be replaced by any heat treatment method including an electric furnace heating method.

Claims (6)

반도체 발광소자용 발광층 형성방법에 있어서,In the light emitting layer forming method for a semiconductor light emitting device, 실리콘 기판(1)에 실리콘 산화막(2)을 형성하는 제1단계와,A first step of forming a silicon oxide film 2 on the silicon substrate 1, 상기 제1단계의 산화막(2) 내부에 점결함(4)을 과잉 발생시키기 위하여 실리콘 이온(3)을 이온주입하는 제2단계와,A second step of ion implanting silicon ions 3 to excessively generate point defects 4 in the oxide film 2 of the first step; 상기 제2단계의 점결함(4)과 실리콘 원자들이 결합하여 산화막(2) 내부에 극미세 실리콘 결정립(5)을 형성하여 강한 적색 발광을 유기시키도록 하기 위하여 질소분위기하에서 열처리하는 제3단계를 포함하는 실리콘 발광소자용 발광층 형성방법.And a third step of heat-treating under a nitrogen atmosphere to bond the point defects (4) of the second step and the silicon atoms to form ultrafine silicon crystal grains (5) inside the oxide film (2) to induce strong red light emission. Method of forming a light emitting layer for a silicon light emitting device. 제1항에 있어서, 상기 제1단계의 산화막 형성은 습식 산화법인 것을 특징으로 하는 실리콘 발광소자용 발광층 형성방법.The method of claim 1, wherein the oxide film is formed by a wet oxidation method. 제1항에 있어서, 상기 제2단계의 주입되는 이온은 과잉 점결함 발생이 가능한 이온을 특징으로 하는 실리콘 발광 소자용 발광층 형성방법.The method of claim 1, wherein the ions implanted in the second step are ions capable of generating excessive point defects. 제1항 또는 제3항에 있어서, 상기 제2단계의 실리콘 이온주입량은 1 × 1017/cm2미만의 도우즈(dose)인 것을 특징으로 하는 실리콘 발광소자용 발광층 형성방법.4. The method of claim 1, wherein the amount of silicon ions implanted in the second step is a dose of less than 1 × 10 17 / cm 2. 5 . 제1항에 있어서, 상기 제3단계의 열처리는 통상의 전기로 가열법인 것을 특징으로 하는 실리콘 발광소자용 발광층 형성방법.The method of claim 1, wherein the heat treatment in the third step is a conventional electric furnace heating method. 제1항 또는 제5항에 있어서, 상기 제3단계의 열처리는 12시간 이상 열처리를 수행하는 것을 특징으로 하는 실리콘 발광소자용 발광층 형성방법.6. The method of claim 1 or 5, wherein the heat treatment in the third step is performed for at least 12 hours.
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