• 한국재료학회:학술대회논문집
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• 한국재료학회 2010년도 춘계학술발표대회
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• pp.35.2-35.2
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• 2010

최근 $Cu(In,Ga)Se_2$(CIGS)와 같은 박막 태양전지에 대한 연구가 많은 관심을 끌고 있다. CIGS 태양전지의 광투과층으로 사용되고 있는 II-VI족 화합물 반도체인 CdS는 상온에서의 에너지 밴드 갭(band gap)이 2.42eV 정도로서, 가시광영역의 많은 빛을 투과시키고, 적절한 제작 조건하에서 비교적 낮은 비저항을 나타내기 때문에 널리 사용되고 있다. 하지만 CIGS 태양전지 연구는 주로 CIGS 흡수층 제조공정에 편중되어 있으며, CdS 버퍼층 공정조건에 대한 체계적인 연구가 부족하다고 판단된다. 습식공정인 Chemical Bath Deposition (CBD)에 의해 주로 제조되는 CdS는 단순한 제조공정에도 불구하고 CIGS 태양전지의 성능에 지대한 영향을 미치는 것으로 알려져 있다. 특히, CdS합성반응이 개시되기 전까지의 용액잔류시간 (dip time)은 CIGS내로의 Cd이온 농도를 결정하는 중요한 공정변수로 판단된다. CIGS 표면에 Cd이 도핑될 경우, CIGS는 n형 전도성을 갖는 얇은 층을 갖게 되어 전체적으로 n-CIGS/p-CIGS의 동종 접합을 형성하는 장점을 부여할 것으로 기대된다. 따라서 본 논문에서는 dip time을 주요변수로 하여 CIGS 태양전지의 성능에 미치는 영향을 주로 고찰하였다. Cd의 확산 정도는 secondary ion mass spectroscopy (SIMS)를 이용하여 정량화하였으며, 제조된 CIGS 태양전지의 전류-전압 특성과 상관성을 제시하고자 한다.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2010년도 춘계학술대회 초록집
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• pp.101.1-101.1
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• 2010

$Cu(InGa)Se_2$ (CIGS) 태양전지는 박막형 태양전지 중 가장 높은 에너지 변환 효율이 보고 되고 있다. CIGS 태양전지를 제조하는 방법은 3 단계 동시 증착법, 금속 전구체의 셀렌화 공정법, 전기 증착법 등이 있다. 이 중 금속 전구체의 셀렌화 공정법은 다른 제조 방법에 비해 대면적 생산에 유리하고, 비교적 공정 과정이 간단하다는 장점이 있다. 하지만 금속 전구체의 미세구조 및 제조 방법, 셀렌화 공정의 최적화에 대한 연구가 부족하다. 본 실험에서는 후면전극으로 사용되는 Mo 층이 증착된 소다회 유리(soda-lime glass)를 기판으로 사용하였다. Cu-In(4:6), Cu-Ga(6:4) 타겟을 DC 스퍼터링 시스템을 이용하여 금속 전구체를 증착하였다. 이 후 미국 Delawere 대학교의 IEC 연구소와 한국전자통신연구원 (ETRI)에서 금속 전구체의 셀렌화 공정을 진행하였다. 셀렌화 공정 전후의 금속 전구체의 결정 크기와 미세구조의 변화를 관찰하기 위하여 주사전자현미경 (SEM)과 X선 회절 분석기 (XRD)를 사용하였다. 센렌화 공정이 진행된 금속 전구체 위에 버퍼층으로 사용되는 CdS와 전면전극으로 사영되는 ZnO, ITO 층을 합성한 후 에너지 변환 효율을 측정하였다. 최고 효율은 9.7%로 관찰되었다.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2001년도 추계학술대회 논문집 Vol.14 No.1
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• pp.167-170
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• 2001

The stochiometric mix of evaporating materials for the $CdGa_{2}Se_{4}$ single crystal thin films was prepared from horizontal furnace. To obtain the single crystal thin films, $CdGa_{2}Se_{4}$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the Hot Wall Epitaxy (HWE) system. The source and substrate temperature were $630^{\circ}C$ and $420^{\circ}C$, respectively. The crystalline structure of single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). The carrier density and mobility of $CdGa_{2}Se_{4}$ single crystal thin films measured from Hall effect by van der Pauw method are $8.27{\times}10^{17}cm^{-3},345cm^{2}/V{\cdot}s$ at 293 K, respectively. From the photocurrent spectrum by illumination of perpendicular light on the c-axis of the $CuInSe_{2}$ single crystal thin film, we have found that the values of spin orbit splitting $\Delta$ So and the crystal field splitting $\Delta$Cr were 106.5 meV and 418.9 meV at 10 K, respectively. From the photoluminescence measurement on $CdGa_{2}Se_{4}$ single crystal thin film, we observed free excition (Ex) existing only high Quality crystal and neutral bound exiciton $(D^{0},X)$ having very strong peak intensity. Then, the full-width-at-half-maximum(FWHM) and binding energy of neutral donor bound excition were 8 meV and 13.7 meV, respectivity. By Haynes rule, an activation energy of impurity was 137 meV.

• 한국전기전자재료학회:학술대회논문집
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• 한국전기전자재료학회 2001년도 추계학술대회 논문집
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• pp.167-170
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• 2001

The stochiometric mix of evaporating materials for the CdGa$_2$Se$_4$ single crystal thin films was prepared from horizontal furnace. To obtain the single crystal thin films, CdGa$_2$Se$_4$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the Hot Wall Epitaxy (HWE) system. The source and substrate temperature were 630$^{\circ}C$ and 420$^{\circ}C$, respectively. The crystalline structure of single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). The carrier density and mobility of CdGa$_2$Se$_4$ single crystal thin films measured from Hall erect by van der Pauw method are 8.27x10$\^$17/ cm$\^$-3/, 345 $\textrm{cm}^2$/V$.$s at 293 K, respectively. From the Photocurrent spectrum by illumination of perpendicular light on the c-axis of the CuInSe$_2$ single crystal thin film, we have found that the values of spin orbit splitting ΔSo and the crystal field splitting ΔCr were 106.5 meV and 418.9 meV at 10 K, respectively. From the photoluminescence measurement on CdGa$_2$Se$_4$ single crystal thin film, we observed free excition (E$\_$X/) existing only high quality crystal and neutral bound exiciton (D$\^$0/,X) having very strong peak intensity. Then, the full-width-at-half-maximum(FWHM) and binding energy of neutral donor bound excision were 8 meV and 13.7 meV, respectivity. By Haynes rule, an activation energy of impurity was 137 meV,

• Current Photovoltaic Research
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• 제3권2호
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• pp.54-60
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• 2015

ZnSnO thin films were deposited by atomic layer deposition (ALD) process using diethyl zinc ($Zn(C_2H_5)_2$) and tetrakis (dimethylamino) tin ($Sn(C_2H_6N)_4$) as metal precursors and water vapor as a reactant. ALD process has several advantages over other deposition methods such as precise thickness control, good conformality, and good uniformity for large area. The composition of ZnSnO thin films was controlled by varying the ratio of ZnO and $SnO_2$ ALD cycles. The ALD ZnSnO film was an amorphous state. The band gap of ZnSnO thin films increased as the Sn content increased. The CIGS solar cell using ZnSnO buffer layer showed about 18% energy conversion efficiency. With such a high efficiency with the ALD ZnSnO buffer and no light soaking effect, AlD ZnSnO buffer mighty be a good candidate to replace Zn(S,O) buffer in CIGSsolar cells.

• 한국진공학회:학술대회논문집
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• 한국진공학회 2014년도 제46회 동계 정기학술대회 초록집
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• pp.472.1-472.1
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• 2014

현재 Cu(In,Ga)Se2나 Cu2ZnSn(S,Se)4 (CZTSSe)계 박막태양전지의 버퍼층으로 가장 많이 사용되는 물질은 CdS이다. 하지만 Cd의 독성 문제로 인해 사용에 제약이 있고, CdS의 작은 밴드갭(~2.4 eV)으로 인해 단 파장 영역에서 광활성층의 빛 흡수를 저해하는 문제 때문에 새로운 대체 물질을 찾으려는 연구가 많이 이루어지고 있다. 이러한 관점에서, ZnS계 물질은 독성 원소인 Cd을 사용하지 않고, 3.6 eV 정도의 큰 밴드갭을 가지기 때문에, CdS 버퍼층을 대체하기 위한 물질로 관심을 받고 있다. ZnS계 버퍼층을 증착하는 위해 chemical bath deposition (CBD), molecular beam epitaxy (MBE), thermal evaporation, spray pyrolysis, sputtering, elecrtrodepostion 등의 다양한 공정이 사용될 수 있다. 본 연구에서는 상기의 다양한 공정 가운데, 공정 단가가 낮고, 대면적 공정에 용이한 CBD 공정을 이용하여 ZnS계 버퍼층을 증착하는 연구를 수행하였다. 용액의 조성, 농도, 공정 온도, 시간 등을 비롯한 다양한 공정 변수가 ZnS계 박막의 morphology, 조성, 결정성, 광학적 특성 등 다양한 특성에 미치는 영향이 체계적으로 연구되었다. 또한, 상기 ZnS계 버퍼층을 CZTSSe 박막태양전지에 적용하여 CdS를 성공적으로 대체할 수 있음을 확인하였다. 본 연구를 통하여 ZnS계 버퍼층이 향후 친환경적인 박막태양전지 제조에 활용될 수 있는 가능성을 확인할 수 있었다.

• 한국신재생에너지학회:학술대회논문집
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• 한국신재생에너지학회 2006년도 춘계학술대회
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• pp.152-153
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• 2006

The new approach to buffer layer design for CIGS solar cells that permitted to reduce the buffer absorption losses in the short wavelength range and to overcome the disadvantages inherent to Cd-free CIGS solar cells was proposed. A chemical bath deposition method has been used to produce a high duality buffer layer that comprises thin film of CdS and Zn-based film. The double layer was grown on either ITO or CIGS substrates and its morphological, structural and optical properties were characterized. The Zn-based film was described as the ternary compound $ZnS_x(OH)_y$. The composition of the $ZnS_x(OH)_y$ layer was not uniform throughout its thickness. $ZnS_x(OH)_y$/CdS/substrate region was a highly intermixed region with gradually changing composition. The short wavelength cut-off of double layer was shifted to shorter wavelength (400nm) compared to that (520 nm) for the standard CdS by optimization of the double buffer design. The results show the way to improve the light energy collection efficiency of the nearly cadmium-free CIGS-based solar cells.

• 한국전기전자재료학회논문지
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• 제14권6호
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• pp.445-454
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• 2001

The stochiometric mix of evaporating materials for the CuInSe$_2$ single crystal thin films was prepared from horizontal furnace. To obtain the single crystal thin films, CuInSe$_2$ mixed crystal was deposited on thoroughly etched semi-insulating GaAs(100) substrate by the Hot Wall Epitaxy(HWE) system. The source and substrate temperature were 62$0^{\circ}C$ and 41$0^{\circ}C$, respectively. The crystalline structure of single crystal thin films was investigated by the photoluminescence and double crystal X-ray diffraction (DCXD). The carrier density and mobility of CuInSe$_2$ single crystal thin films measured from Hall effect fby van der Pauw method are 9.62x10$^{16}$ cm$^{-3}$ , 296$\textrm{cm}^2$/V.s at 293 K, respectively. From the photocurrent spectrum by illumination of perpendicular light on the c-axis of the CuInSe$_2$ single crystal thin film we have found that he values of spin orbit splitting ΔSo and the crystal field splitting ΔCr were 6.1 meV and 175.2 meV at 10K, respectively. From the photoluminescence measurement on CuInSe$_2$ single crystal thin film we observed free excition (Ex) existing only high quality crystal and neutral bound exiciton (D$^{\circ}$,X) having very strong peak intensity. Then, the full-width-at-half-maximum(FWHM) and binding energy of neutral donor bound excition were 7meV and 5.9meV, respectivity. by Haynes rule, an activation energy of impurity was 50 meV.

• ETRI Journal
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• 제38권2호
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• pp.265-271
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• 2016

We analyzed the interface characteristics of Zn-based thin-film buffer layers formed by a sulfur thermal cracker on a $Cu(In,Ga)Se_2$ (CIGS) light-absorber layer. The analyzed Zn-based thin-film buffer layers are processed by a proposed method comprising two processes - Zn-sputtering and cracker-sulfurization. The processed buffer layers are then suitable to be used in the fabrication of highly efficient CIGS solar cells. Among the various Zn-based film thicknesses, an 8 nm-thick Zn-based film shows the highest power conversion efficiency for a solar cell. The band alignment of the buffer/CIGS was investigated by measuring the band-gap energies and valence band levels across the depth direction. The conduction band difference between the near surface and interface in the buffer layer enables an efficient electron transport across the junction. We found the origin of the energy band structure by observing the chemical states. The fabricated buffer/CIGS layers have a structurally and chemically distinct interface with little elemental inter-diffusion.

• 한국재료학회지
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• 제31권11호
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• pp.619-625
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• 2021

Cu₂ZnSn(S,Se)₄ (CZTSSe) based thin-film solar cells have attracted growing attention because of their earth-abundant and non-toxic elements. However, because of their large open-circuit voltage (V_oc)-deficit, CZTSSe solar cells exhibit poor device performance compared to well-established Cu(In,Ga)(S,Se)₂ (CIGS) and CdTe based solar cells. One of the main causes of this large V_oc-deficit is poor absorber properties for example, high band tailing properties, defects, secondary phases, carrier recombination, etc. In particular, the fabrication of absorbers using physical methods results in poor surface morphology, such as pin-holes and voids. To overcome this problem and form large and homogeneous CZTSSe grains, CZTSSe based absorber layers are prepared by a sputtering technique with different RTA conditions. The temperature is varied from 510 ℃ to 540 ℃ during the rapid thermal annealing (RTA) process. Further, CZTSSe thin films are examined with X-ray diffraction, X-ray fluorescence, Raman spectroscopy, IPCE, Energy dispersive spectroscopy and Scanning electron microscopy techniques. The present work shows that Cu-based secondary phase formation can be suppressed in the CZTSSe absorber layer at an optimum RTA condition.