KR100372752B1 - Manufacturing method and apparatus of CdS film - Google Patents
Manufacturing method and apparatus of CdS film Download PDFInfo
- Publication number
- KR100372752B1 KR100372752B1 KR10-2000-0026610A KR20000026610A KR100372752B1 KR 100372752 B1 KR100372752 B1 KR 100372752B1 KR 20000026610 A KR20000026610 A KR 20000026610A KR 100372752 B1 KR100372752 B1 KR 100372752B1
- Authority
- KR
- South Korea
- Prior art keywords
- substrate
- solution
- cds
- ions
- temperature
- Prior art date
Links
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 19
- 229910052980 cadmium sulfide Inorganic materials 0.000 claims abstract description 77
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 claims abstract description 70
- 239000000758 substrate Substances 0.000 claims abstract description 60
- 150000002500 ions Chemical class 0.000 claims abstract description 50
- 239000010408 film Substances 0.000 claims abstract description 46
- 238000000034 method Methods 0.000 claims abstract description 23
- 239000002245 particle Substances 0.000 claims abstract description 12
- 238000010438 heat treatment Methods 0.000 claims abstract description 11
- 239000010409 thin film Substances 0.000 claims abstract description 9
- 230000015572 biosynthetic process Effects 0.000 claims abstract description 7
- 230000006911 nucleation Effects 0.000 claims description 8
- 238000010899 nucleation Methods 0.000 claims description 8
- 238000000151 deposition Methods 0.000 claims description 5
- 239000012528 membrane Substances 0.000 claims description 5
- 230000008021 deposition Effects 0.000 claims description 4
- 239000011491 glass wool Substances 0.000 claims description 2
- 238000001179 sorption measurement Methods 0.000 claims description 2
- 238000003756 stirring Methods 0.000 claims 1
- 238000000224 chemical solution deposition Methods 0.000 abstract description 15
- 238000006243 chemical reaction Methods 0.000 abstract description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 abstract description 2
- 229910052793 cadmium Inorganic materials 0.000 abstract description 2
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 abstract description 2
- 230000007423 decrease Effects 0.000 abstract description 2
- 229910052717 sulfur Inorganic materials 0.000 abstract description 2
- 239000011593 sulfur Substances 0.000 abstract description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 7
- 238000005755 formation reaction Methods 0.000 description 6
- 229910004613 CdTe Inorganic materials 0.000 description 3
- 238000002834 transmittance Methods 0.000 description 2
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000002542 deteriorative effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000007788 roughening Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000005118 spray pyrolysis Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 238000007738 vacuum evaporation Methods 0.000 description 1
Classifications
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/036—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes
- H01L31/0392—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate
- H01L31/03925—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by their crystalline structure or particular orientation of the crystalline planes including thin films deposited on metallic or insulating substrates ; characterised by specific substrate materials or substrate features or by the presence of intermediate layers, e.g. barrier layers, on the substrate including AIIBVI compound materials, e.g. CdTe, CdS
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
- H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
- H01L31/0264—Inorganic materials
- H01L31/0296—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe
- H01L31/02966—Inorganic materials including, apart from doping material or other impurities, only AIIBVI compounds, e.g. CdS, ZnS, HgCdTe including ternary compounds, e.g. HgCdTe
-
- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
- H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
- H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
Abstract
본 발명은 CBD(Chemical bath deposition)법을 이용하여 황화카드뮴(CdS) 박막을 제조함에 있어서, 카드뮴(Cd) 이온과 황(S) 이온이 용해되어 있는 용액을 가열시키는 열원을 기판의 상부에 설치함으로써 기판에서 Cd 이온과 S 이온이 반응하여 CdS 막을 형성하는 CdS막의 제조방법 및 장치에 관한 것이다.In the present invention, in manufacturing a cadmium sulfide (CdS) thin film using a chemical bath deposition (CBD) method, a heat source for heating a solution in which cadmium (Cd) ions and sulfur (S) ions are dissolved is installed on an upper portion of a substrate. The present invention relates to a method and apparatus for producing a CdS film in which Cd ions and S ions react with each other to form a CdS film.
본 발명은 용액에 함침되어 있는 기판 상부에 용액을 가열시키는 열원인 히터를 설치하여 기판이 가장 높은 온도를 갖도록 하고, 용액의 온도는 기판에서 멀어질수록 감소하게 함으로써 기판부근의 용액중에서 Cd 이온과 S 이온이 반응하여 CdS 입자의 생성을 억제하는 동시에 기판에서 Cd 이온과 S 이온이 반응하여 CdS 막이 생성되는 불균일 반응을 촉진하고 CdS막의 성장을 증가시키는 것을 목적으로 한다.The present invention is to install a heater that is a heat source for heating the solution on top of the substrate impregnated with the solution so that the substrate has the highest temperature, and the temperature of the solution decreases as it moves away from the substrate to reduce the Cd ions in the solution near the substrate. The purpose of the present invention is to promote the heterogeneous reaction in which Sd ions react to suppress the formation of CdS particles and to react with Cd ions and S ions on a substrate to form a CdS film and to increase the growth of the CdS film.
Description
본 발명은 CBD(Chemical bath deposition)법을 이용하여 황화카드뮴(CdS) 박막을 제조함에 있어서, 카드뮴(Cd) 이온과 황(S) 이온이 용해되어 있는 용액을 가열시키는 열원을 기판의 상부에 설치함으로써 기판에서 Cd 이온과 S 이온이 반응하여 CdS 막을 형성하는 CdS막의 제조방법 및 장치에 관한 것이다.In the present invention, in manufacturing a cadmium sulfide (CdS) thin film using a chemical bath deposition (CBD) method, a heat source for heating a solution in which cadmium (Cd) ions and sulfur (S) ions are dissolved is installed on an upper portion of a substrate. The present invention relates to a method and apparatus for producing a CdS film in which Cd ions and S ions react with each other to form a CdS film.
CdS는 2.42eV의 밴드 갭(band gap)을 가지는 직접천이형 반도체로서 CdTe계 태양전지와 CIS(CuInSe2)계 태양전지의 접합 파트너(junction partner)로 많이 이용되어 왔다. 태양전지에서 광투과 층으로 사용되는 CdS 막은 높은 광투과도를 가지기 위해 두께가 얇으면서도, 누설전류(leakage current)가 발생하지 않을 정도의 치밀함을 가져야한다.CdS is a direct transition semiconductor having a band gap of 2.42 eV and has been widely used as a junction partner of CdTe based solar cells and CIS (CuInSe 2 ) based solar cells. The CdS film used as the light transmitting layer in the solar cell has to be thin enough to have a high light transmittance and yet have a compactness such that leakage current does not occur.
CdS막을 제조하는 방법으로는 spray pyrolysis, vacuum evaporation, chemical bath deposition(CBD)법 등의 방법이 이용되고 있다. 이중 CBD법은 용액 내에서 일어나는 화학반응을 이용하는 박막제조 방법으로 낮은 온도에서 막의 제조가 가능하고, 제조방법이 간단하며, 제조비가 저렴하다는 장점이 있다.As a method of manufacturing a CdS film, methods such as spray pyrolysis, vacuum evaporation, and chemical bath deposition (CBD) are used. The CBD method is a thin film manufacturing method using a chemical reaction occurring in a solution, it is possible to manufacture the film at a low temperature, the manufacturing method is simple, and the manufacturing cost is low.
CBD 법의 CdS막 형성반응은 용액 중에서 Cd 이온과 S 이온이 반응하여 생성된 CdS가 기판에 달라붙어 CdS막이 생성되는 균일 반응(homogeneous reaction)과, 기판 위에서 Cd 이온과 S 이온이 반응하여 CdS막이 생성되는 불균일 반응(heterog eneous reaction)으로 나눌 수 있는데 양질의 CdS막을 얻기 위해서는 기판에서 Cd 이온과 S 이온이 반응하여 CdS막이 생성되는 불균일 반응이 촉진되는 것이 바람직하다.The CdS film formation reaction of the CBD method is a homogeneous reaction in which CdS formed by reacting Cd ions and S ions in a solution adheres to a substrate, thereby forming a CdS film, and a CdS film is formed by reacting Cd ions and S ions on a substrate. It can be divided into a heterogeneous reaction (heterog eneous reaction). In order to obtain a high quality CdS film, it is preferable to promote a heterogeneous reaction in which a CdS film is formed by reacting Cd ions and S ions on a substrate.
종래의 화학 용액 성장법(CBD)으로 CdS 박막을 제조할 경우 Cd 이온과 S 이온이 포함되어 있는 용액을 가열하는 열원은 오일 용기 내의 히터를 통해서이다. 따라서 기판보다 용액의 온도가 더욱 높으므로, 용액 중에서 Cd 이온과 S 이온이 반응하여 생성된 CdS가 기판에 달라붙어 CdS 막이 생성되는 균일 반응(homogeneous reaction)이 활발하게 일어난다. 이 공정을 사용할 경우 증착된 CdS막의 표면에는 용액 내에서 핵 생성되어 성장한 CdS 입자(particle)가 CdS 막의 표면에 붙게 되어 CdS막의 표면이 거칠어지고, 그 후의 공정에 의해 CdS막 표면의 CdS 입자가 제거될 경우 핀홀(pinhole)이 형성되며 이러한 핀홀은 CdTe층과의 접합특성을 저하시키고 누설전류(leakage current)를 증가시키는 문제점이 있다.When manufacturing a CdS thin film by the conventional chemical solution growth method (CBD), the heat source for heating a solution containing Cd ions and S ions is through a heater in an oil container. Therefore, since the temperature of the solution is higher than that of the substrate, a homogeneous reaction in which CdS generated by reacting Cd ions and S ions in the solution adheres to the substrate and generates a CdS film is actively performed. In this process, CdS particles nucleated and grown in solution adhere to the surface of the CdS film on the surface of the deposited CdS film, thereby roughening the surface of the CdS film, and subsequently removing CdS particles on the surface of the CdS film. If pinholes are formed, these pinholes have a problem of deteriorating the bonding characteristics with the CdTe layer and increasing leakage current.
본 발명은 상기의 문제점을 해결하기 위하여 용액에 함침되어 있는 기판 상부에 용액을 가열시키는 열원인 히터를 설치하여 기판이 가장 높은 온도를 갖도록 하고, 용액의 온도는 기판에서 멀어질수록 감소하게 함으로써 기판부근의 용액중에서 Cd 이온과 S 이온이 반응하여 CdS 입자의 생성을 억제하는 동시에 기판에서 Cd 이온과 S 이온이 반응하여 CdS 막이 생성되는 불균일 반응을 촉진하고 CdS막의 성장을 증가시키는 것을 목적으로 한다.The present invention is to solve the above problems by installing a heater that is a heat source for heating the solution on top of the substrate impregnated with the solution so that the substrate has the highest temperature, so that the temperature of the solution decreases away from the substrate Cd ions and S ions react in a nearby solution to suppress the formation of CdS particles, and at the same time, to promote a heterogeneous reaction in which a CdS film is formed by reacting Cd ions and S ions on a substrate and to increase the growth of the CdS film.
도 1(a)(b)은 본 발명에 의해 제작한 CdS막의 표면 SEM(Scanning Electron Micrograph) 사진이고,Figure 1 (a) (b) is a SEM (Scanning Electron Micrograph) photograph of the CdS film produced by the present invention,
도 1(c)은 본 발명에 의해 제작한 CdS막의 단면을 나타낸 SEM 사진이다.Fig. 1C is a SEM photograph showing a cross section of the CdS film produced according to the present invention.
도 2는 종래의 방법을 이용하여 제작한 CdS막의 표면을 나타낸 SEM 사진으로Figure 2 is a SEM photograph showing the surface of the CdS film produced using a conventional method
(a)는 용액온도를 60℃인 경우(a) is the solution temperature of 60 ℃
(b)는 용액온도를 70℃인 경우(b) is the solution temperature of 70 ℃
(c)는 용액온도를 80℃인 경우(c) is the solution temperature of 80 ℃
(d)는 용액온도를 90℃인 경우(d) is the solution temperature of 90 ℃
도 3은 본 발명의 CdS막의 제조시 사용하는 장치이다.3 is an apparatus used in the production of the CdS film of the present invention.
일반적으로 CBD법을 사용하여 CdS막을 증착시 용액 중에서 다음과 같은 반응이 일어난다.In general, when a CdS film is deposited using the CBD method, the following reaction occurs in a solution.
(1) NH4(CH3COO) ⇔ CH3COO-+ NH4 + (1) NH 4 (CH 3 COO) ⇔ CH 3 COO - + NH 4 +
(2) Cd(CH3COO) ⇔ 2CH3COO-+ Cd2+ (2) Cd (CH 3 COO ) ⇔ 2CH 3 COO - + Cd 2+
(3) NH3+ H2O ⇔ NH4 ++ OH- (3) NH 3 + H 2 O ⇔ NH 4 + + OH -
(4) Cd2++2OH-⇔ Cd(OH)2(S)(4) Cd 2+ + 2OH - ⇔ Cd (OH) 2 (S)
(5) Cd2++4NH3⇔ Cd(NH3)4 2+ (5) Cd 2+ + 4NH 3 ⇔ Cd (NH 3) 4 2+
(6) (NH2)2CS + 2OH-⇔ S2-+ 2H2O + H2CN2 (6) (NH 2 ) 2 CS + 2OH - ⇔ S 2- + 2H 2 O + H 2 CN 2
(7) Cd2++S2-⇔ CdS (S)(7) Cd 2+ + S 2- ⇔ CdS (S)
상기에서 Cd(CH3COO)2와 (NH2)2CS는 각각 Cd 이온과 S 이온의 공급원이며 NH4(CH3COO)는 용액의 완충제(buffer)로서 작용하고 NH3는 용액의 pH를 조절한다. CdS 막의 형성은 용액 내의 Cd 이온의 농도와 S 이온의 농도의 곱이 각 온도에서 용액의 용해도 곱보다 큰 경우에 이루어진다.Where Cd (CH 3 COO) 2 and (NH 2 ) 2 CS are sources of Cd ions and S ions, respectively, and NH 4 (CH 3 COO) acts as a buffer for the solution and NH 3 is the pH of the solution. Adjust The formation of the CdS film occurs when the product of the concentration of Cd ions and the concentration of S ions in the solution is greater than the product of solubility of the solution at each temperature.
본 발명은 CBD법을 이용하여 CdS 박막을 제조함에 있어서, 종래 기판을 가열하는 열원(heat source)을 기판의 측면 또는 하부에 위치하는 것과 달리 기판을 가열하는 열원을 기판 상부에 설치하여 열(heat)을 발생시켜 먼저 기판을 가열한 후용액 중으로 전달함으로서 용액중의 Cd 이온과 S 이온이 반응하여 용액중에서 CdS 입자(particle)를 생성하는 것을 억제하는 한편, 용액중의 Cd 이온과 S 이온이 기판에서 반응하여 CdS막을 형성하는 것을 특징으로 한다.According to the present invention, in manufacturing a CdS thin film using the CBD method, a heat source for heating a substrate is installed on the substrate, whereas a heat source for heating the substrate is positioned on a side or a bottom of the substrate. C) ions and S ions in the solution react to prevent the formation of CdS particles in the solution, while the substrate is first heated and then transferred to the solution, while Cd ions and S ions in the solution Reacting at to form a CdS film.
상기에서 Cd 이온과 S 이온이 함유된 용액의 온도는 CdS 핵생성이 잘 이루어지지 않는 40∼60℃의 온도로 유지하고, 기판의 온도는 CdS 핵생성이 잘 이루어지는 100∼150℃로 유지하게끔 열원을 조절하여 불균일 핵생성이 일어나기 위해 기판과 접촉된 아주 소량의 용액 온도만 기판 온도와 비슷한 값을 갖도록 한다. 또한 기판 및 기판의 상부에 위치한 열원을 모터와 같은 회전장치와 연결하여 기판 및 열원을 회전할 수 있도록 하여 기판에서의 CdS막 증착 속도를 증가시킬 수 있으며 보다 균일한 CdS 핵이 기판에서 생성될 수 있도록 한다.The temperature of the solution containing the Cd ions and S ions is maintained at a temperature of 40 ~ 60 ℃ that CdS nucleation is not good, and the temperature of the substrate to maintain a temperature of 100 ~ 150 ℃ that CdS nucleation is good By adjusting the temperature, only a very small solution temperature in contact with the substrate in order for heterogeneous nucleation to occur is similar to the substrate temperature. In addition, the substrate and the heat source located on top of the substrate can be connected with a rotating device such as a motor to rotate the substrate and the heat source, thereby increasing the deposition rate of the CdS film on the substrate, and a more uniform CdS nucleus can be generated on the substrate. Make sure
또한 상기의 기판 및 열원을 회전시켜 CdS막의 증착 속도를 증가시키는 방법 이외에 기판을 미리 100∼200℃의 온도로 가열한 후 용액내부로 주입하면 기판의 온도가 높은 이유로 기판에서 Cd 이온과 S 이온의 반응이 빨리 이루어져 기판에서의 CdS막의 불균인 핵생성 속도를 증가시킬 수 있으며, 종래 CBD법에서 사용되었던 오일 히터(oil heater)로 용액의 온도를 미리 40-60℃까지 가열하여 기판에서의 CdS막의 증착시간을 감소시키고 용액중에서 CdS 입자의 생성을 억제할 수 있다.In addition to the method of increasing the deposition rate of the CdS film by rotating the substrate and the heat source, if the substrate is heated to a temperature of 100 to 200 ° C. and then injected into the solution, the Cd ions and S ions of the substrate The reaction can be accelerated to increase the uneven rate of nucleation of the CdS film on the substrate, and the temperature of the solution is heated to 40-60 ° C. in advance using an oil heater used in the conventional CBD method. The deposition time can be reduced and the formation of CdS particles in the solution can be suppressed.
한편 용액 중에서 Cd 이온과 S 이온이 반응하여 생성되는 CdS 입자가 기판위에 흡착되는 것을 방지하기 위하여 Cd 이온과 S 이온이 함유된 용액이 채워진 용기외부에 초음파 진동장치를 구비하여 이것에 의해 발생되는 초음파를 용액 내로 전달시킴으로써 용액 중에서 형성된 CdS 입자가 CdS막에 부착되는 것을 억제한다.On the other hand, in order to prevent the adsorption of CdS particles generated by the reaction of Cd ions and S ions in the solution on the substrate, an ultrasonic vibration device is provided outside the container filled with the solution containing Cd ions and S ions. The CdS particles formed in the solution are suppressed from adhering to the CdS film by transferring the into the solution.
본 발명의 CdS 박막 제조시 사용하는 장치는 도 3과 같이 기판홀더(8)에 의해 지지되는 기판(7)의 상부에 열원(6)을 구비하는 한편 열원(6)에 의해 장치상부가 가열되는 것을 억제하기 위해 열원(6) 위에 유리솜(5)을 구비한 것을 특징으로 한다.The apparatus used for manufacturing the CdS thin film of the present invention has a heat source 6 on the substrate 7 supported by the substrate holder 8 as shown in FIG. 3 while the upper part of the device is heated by the heat source 6. In order to suppress this, the glass wool 5 is provided on the heat source 6, It is characterized by the above-mentioned.
도 3에서 도면부호 1은 기판의 온도를 측정하기 위한 열전대이고, 도면부호 2는 용액의 온도를 측정하기 위한 열전대이고, 도면부호 4는 테프론으로 제작된 덮개이고, 도면부호 9는 용액이고, 도면부호 10은 스티러(stirrer)를 나타낸다.In Figure 3, reference numeral 1 is a thermocouple for measuring the temperature of the substrate, 2 is a thermocouple for measuring the temperature of the solution, 4 is a cover made of Teflon, 9 is a solution, Reference numeral 10 denotes a stirrer.
이하 본 발명을 다음의 시험예에 의하여 설명하고자 한다. 그러나 이것이 본 발명의 기술적 범위를 한정하는 것은 아니다.Hereinafter, the present invention will be described by the following test examples. However, this does not limit the technical scope of the present invention.
<실시예><Example>
도 3의 장치로 CBD 방법을 이용하여 본 발명의 CdS 막을 제조하기 위하여 Cd 이온과 S 이온의 공급원으로 각각 Cd(CH3COO)20.01 mole과 (NH2)2CS 0.02 mole을 사용하고 용액의 완충제는 NH4(CH3COO) 0.02 mole을 사용하여 CdS 막을 제조하기 위한 용액의 준비를 하였다.In order to prepare a CdS membrane of the present invention using the CBD method with the apparatus of FIG. 3, Cd (CH 3 COO) 2 0.01 mole and (NH 2 ) 2 CS 0.02 mole were used as sources of Cd ions and S ions, respectively. The buffer was prepared with a solution to prepare a CdS membrane using 0.02 mole of NH 4 (CH 3 COO).
기판 상부에 위치한 열원으로 기판을 가열하여 기판온도를 120℃로 세팅(set ting)하고 상기에서 언급한 용액을 45℃로 미리 가열시킨 용액에 침지시켰다. 그 후 기판을 외부의 모터와 연결하여 3분에 1회전할 수 있도록 조정하여 기판을 회전시키면서 기판에서 Cd 이온과 S 이온을 반응시켜 CdS막이 생성되도록 하였다. 이때 용액의 최종온도는 70℃ 이하가 되도록 하였다.The substrate was heated with a heat source located above the substrate to set the substrate temperature to 120 ° C. and the solution mentioned above was immersed in a solution previously heated to 45 ° C. Thereafter, the substrate was connected to an external motor and adjusted to rotate once per three minutes, thereby rotating the substrate to react Cd ions and S ions in the substrate to generate a CdS film. At this time, the final temperature of the solution was to be 70 ℃ or less.
도 1은 상기의 방법에 의해 제작한 CdS막의 표면의 5000배(도 1-a), 20000배 (도 1-b) SEM 사진과 단면의 80000배(도 1-c)를 나타낸 SEM 사진으로 사진의 제일 위 부분이 CdS층이고 가운데 부분이 ITO층, 그리고 가장 밑부분이 glass으로 CdS막의 표면에 용액 중에서 성장한 CdS 입자가 매우 적은 양 존재하며 양질의 막이 치밀하게 성장한 것을 알 수 있다.1 is a SEM photograph showing 5000 times (Fig. 1-a), 20000 times (Fig. 1-b) SEM photograph of the surface of the CdS film produced by the above method, and 80000 times (Fig. 1-c) of the cross section. The top of the CdS layer, the center of the ITO layer, and the bottom of the glass is a very small amount of CdS particles grown in solution on the surface of the CdS film, the fine film was grown densely.
도 2(a)(b)(c)(d)는 종래 CBD 방법에 의하여 용액의 온도를 각각 60℃, 70℃, 80℃, 90℃로 하여 제작한 CdS막의 표면 형태를 나타낸 SEM 사진으로 용액의 온도가 증가할수록 CdS막 표면에 용액 중에서 균일핵생성으로 인한 CdS 입자가 다량 존재하며 막이 치밀하지 못한 것을 알 수 있다.2 (a) (b) (c) (d) are SEM images showing the surface morphology of CdS films prepared using the conventional CBD method at 60 ° C., 70 ° C., 80 ° C. and 90 ° C., respectively. It can be seen that as the temperature increases, a large amount of CdS particles due to homogeneous nucleation is present on the surface of the CdS film and the film is not dense.
기존의 CBD법으로 증착한 CdS박막의 경우에 비하여 용액 내에서의 핵생성을 억제하면서도 기판 근처에서만 불균일 핵생성이 일어나도록 제어할 수 있다. 이를 통하여 CdTe와의 접합 특성을 증가시키고, 그 후 공정에서 핀홀(pin hole)의 생성을 저지하여 태양전지의 누설전류를 감소시키고 또한 광투과도를 증가시켜 태양전지의 효율을 증가시킬 수 있다.Compared to the CdS thin film deposited by the conventional CBD method, the nucleation in the solution can be suppressed, and the heterogeneous nucleation can be controlled only near the substrate. Through this, it is possible to increase the bonding characteristics with CdTe, and subsequently to prevent the formation of pin holes in the process to reduce the leakage current of the solar cell and to increase the light transmittance to increase the efficiency of the solar cell.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2000-0026610A KR100372752B1 (en) | 2000-05-18 | 2000-05-18 | Manufacturing method and apparatus of CdS film |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| KR10-2000-0026610A KR100372752B1 (en) | 2000-05-18 | 2000-05-18 | Manufacturing method and apparatus of CdS film |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| KR20010105017A KR20010105017A (en) | 2001-11-28 |
| KR100372752B1 true KR100372752B1 (en) | 2003-02-17 |
Family
ID=45813191
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| KR10-2000-0026610A KR100372752B1 (en) | 2000-05-18 | 2000-05-18 | Manufacturing method and apparatus of CdS film |
Country Status (1)
| Country | Link |
|---|---|
| KR (1) | KR100372752B1 (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100621308B1 (en) | 2004-05-28 | 2006-09-14 | 삼성전자주식회사 | Method of preparing cadmium sulfide nano crystal emitting light at multiple wavelengths and the cadmium sulfide nano crystal prepared by the method |
| KR101035245B1 (en) | 2009-12-04 | 2011-05-19 | 주식회사 디엠에스 | Chemical bath deposition apparatus for manufacturing solar cell |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR20010107798A (en) * | 2001-09-04 | 2001-12-07 | 재 형 이 | Preparation method of the low resistive Cd1-xZnxS thin films using solution growth |
| KR100819121B1 (en) * | 2006-12-06 | 2008-04-03 | 한국전자통신연구원 | Method for formation of cadmium sulfide thin film and cadmium sulfide diode by chemical bath deposition |
| KR100954364B1 (en) * | 2008-04-17 | 2010-04-26 | (주)텔리오솔라코리아 | Apparatus for manufacturing ??-?? compound semiconductor thin film by chemical bath deposition and method thereof |
| KR101360633B1 (en) * | 2012-07-11 | 2014-02-11 | 주식회사 포스코 | Method for manufacturing solar cell having uniform buffer layer and solar cell produced by the same |
| KR101416307B1 (en) * | 2013-03-05 | 2014-07-09 | 군산대학교산학협력단 | Methods and apparatus for thin films deposition |
| CN107142468B (en) * | 2017-07-19 | 2019-07-19 | 成都尚智恒达科技有限公司 | A kind of cadmium sulfide chemical bath plating membrane reactor |
-
2000
- 2000-05-18 KR KR10-2000-0026610A patent/KR100372752B1/en not_active IP Right Cessation
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100621308B1 (en) | 2004-05-28 | 2006-09-14 | 삼성전자주식회사 | Method of preparing cadmium sulfide nano crystal emitting light at multiple wavelengths and the cadmium sulfide nano crystal prepared by the method |
| KR101035245B1 (en) | 2009-12-04 | 2011-05-19 | 주식회사 디엠에스 | Chemical bath deposition apparatus for manufacturing solar cell |
Also Published As
| Publication number | Publication date |
|---|---|
| KR20010105017A (en) | 2001-11-28 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| US8569102B2 (en) | Method of manufacturing high density CIS thin film for solar cell and method of manufacturing thin film solar cell using the same | |
| KR101757897B1 (en) | Bath deposition solution for wet-chemical deposition of a metal sulfide layer and related production method | |
| KR100372752B1 (en) | Manufacturing method and apparatus of CdS film | |
| JP3681870B2 (en) | Method for producing compound semiconductor film and solar cell | |
| CN112289932B (en) | Perovskite film and preparation method and application thereof | |
| CN110473927B (en) | Cuprous oxide/cuprous thiocyanate heterojunction photoelectric film and preparation method thereof | |
| CN113675343A (en) | Perovskite thin film adopting multifunctional group ligand quantum dots and preparation and application thereof | |
| WO2012161402A1 (en) | Method of manufacturing cis-based thin film having high density | |
| Yin et al. | Review of quantum dot deposition for extremely thin absorber solar cells | |
| Di Iorio et al. | Characterization of CuInS 2 thin films prepared by one-step electrodeposition | |
| CN110518081B (en) | Solar cell absorption layer and preparation method and application thereof | |
| Zhao et al. | Sulfurization of electrodeposited Sb/Cu precursors for CuSbS2: potential absorber materials for thin-film solar cells | |
| CN111154484B (en) | MnCIS/ZnS core-shell structure quantum dot material, preparation method thereof and photoelectrochemical cell | |
| KR101137434B1 (en) | Preparation method for cis-based compound thin film by using rapid thermal processing and preparation method for thin film solarcell manufactured by using the cis-based compound thin film | |
| KR101093831B1 (en) | Preparation method of copper indium disulphide thin film for solar cell using spin spray | |
| CN111211224A (en) | Method for quickly preparing commercial perovskite film at low cost | |
| KR101114635B1 (en) | Preparation method of cadmium telluride thin film for solar cell using spray process | |
| JP5792008B2 (en) | Method for manufacturing chalcopyrite solar cell | |
| JP2013016674A (en) | Method for manufacturing buffer layer and photoelectric conversion element including the same | |
| CN111101147B (en) | Preparation method of CoP (cobalt phosphide) nanoparticles on PN junction silicon chip | |
| KR100264232B1 (en) | Method and apparatus for manufacturing cds thin film by chemical bath deposition | |
| KR100954364B1 (en) | Apparatus for manufacturing ??-?? compound semiconductor thin film by chemical bath deposition and method thereof | |
| KR20110092173A (en) | Preparation method of copper indium diselenide thin film for solar cell using continuous flow reaction process | |
| CN105932111A (en) | Method for preparing copper-indium-gallium-selenide photoelectric thin film from copper chloride and gallium chloride | |
| KR101437761B1 (en) | Preparation Method of Copper Selenide Thin Film for Solar Cell Using Continuous Flow Reaction Process |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| A201 | Request for examination | ||
| E902 | Notification of reason for refusal | ||
| E701 | Decision to grant or registration of patent right | ||
| GRNT | Written decision to grant | ||
| FPAY | Annual fee payment |
Payment date: 20060131 Year of fee payment: 4 |
|
| LAPS | Lapse due to unpaid annual fee |