3rd World Conference on Pholovolroie Energv Conversion

May 11-18, 2003 Osaka, Jopnn

30 YEARS TRAJECTORY OF A SOLAR PHOTOVOLTAIC RESEARCH

Yoshihiro Hamakawa Deparrment of Photonics, Faculty of Science and Engineering, Ritsumeikan University 1-1-1 Nojihigashi, Kusatsu, Shiga, 525-8577 Japan Te1:+81-77-561-2871 Fax:+81-77-561-2613 e-mail:hamakawa@se.ritsmnei.ac.jp

ABSTRACT A review is given on a research trajectory of the solar photovoltaic PV science and engineering in recent 30 years. Firstly, an episode of starting the PV research related to the environmental issue is confided, then briefly overviewed with a story how it started the Sunshine Project in 1973. Secondly, a motivation to start the amorphous semiconductor research is explained to fabricate a synthetic semiconductor which could be design the band gap energy. As an example of the material processing, fabrication of the ternaly Si-As-Te amorphous semiconductor in the space by the Space lab J and also amorphous Silicon alloys are introduced together with their essential advantages of the material system in view of both physics and technology as new type of physics semiconductors. Thirdly, as an application of the amorphous silicon material system, a series of high efficiency R & D efforts are demonstrated such as inventions of the a-SiCia-Si heterojunction solar cell and of the stacked solar cells having the junction structures of a-Siiipoly-Si, a-Siiinc-Si etc. .. In the final part of the paper, some new strategies to develop photovoltaic industry in Japan are introduced. The project milestone up to 2010 in the new Sunshine project and present status of the industrializations are summarized and discussed.
1.

Optical Science Center, University of Arizona, and he is famous Astronomer as the discoverer of the Meinel nebula. Then, he explained many things about the new astronomical observatory of the Kit Peak, and most impressive one was an increasing of the sky hazy in recent several years by pollutant gas, even in Tucson Arizona. We had enjoyed so exciting discussions about environment issue with the promotions of industrial development in recent 10 years. Finally he suggests me that that please develop more efficient solar energy conversion technology by semiconductor which should be suhstihlted to fossil fuel. Next morning, He kindly gave me, a kit of his publications on quest of solar energy [3]. On the way back to Japan, I studied very hard to review the materials in the flight seat, and published some review paper entitled Solar Electric Power Generation and A New Role of Semiconductor Technology Challenges to the New Energy - I on the Solar PV, and II on the Solar Photo Thermal conversion [4].
~

2.

THE SUN - SHINE PROJECT AND NEW SUNSHINE PROJECT

MOTIVATION TO START PV RESEARCH

In relation to the State of the Union Message by President Nixon in January and 1973, Japanese AIST, MITl (Agency of Industrial Science and technology, Ministry of International Trade and Industry), had proposed to organize a new initiative namely Sunshine Project (SS) in May

In November 1972, I had an oppomnity to stay at the University of Arizona, Tucson Arizona for attending the I International conference on Modulation Spectroscopy for a week[l]. 1 delivered there an invited review talk on An Oscillatory Franz-Keldish Effect and Modulation Spectroscopy which I established measurement system as an useful new tool for the Characterization of the electronic hand structure parameters of semiconductor which was done mostly at the University of Illinois from 1965 to 1967

PI.
The tale begins at a beautiful evening in the poolside garden party of Professor B. 0. Seraphins home. In the middle of dinner party, I found a bright moving flight object acrossing the twilight sky, and pointed out what is that? Oh, that is an artificial satellite immediately answered the person who sat with next seat of my chair. His name is Professor Aden. B. Meinel, the director of the

Fig.1 3E-Trilemma, the most important task assigned to

21 centurys civilization. Only way to solve it is develop clean technoloav

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3rd World Conference on Photovoltaic Energv Conversion

May 11-18, 2003 Osokn.Japm

3.

.......... .......... ..........

By1560

AMORPHOUS SEMICONDUCTOR RESEARCH FOR LOW COST SOLAR CELL PRODUCTION

New hwhw Rojat

............. ..2 .......... .........

Fig2 Orgnnizations and objectives of the New Sunshine Project 1973, and formally started the project with budget in April 1974. While the first oil shock was in the Middle East began October 1973. The main purpose of the proposal is to bring back clean air and water to our land by new kinds of technological development which is presently said - a solution of 3E-Trile'nma as shown in Fig.1. That is, the regular way along capitalism, for the activation of economical development (E: Economy), we do need an increase of the energy expense ( E Energy). However, it induces environmental issue ( E Environment) by more emissions of pollutant gases. On the contrary, if the political option choses a suppression of pollutant gas emission, it inactivates the economical development. This is 3E-Trilenma. The solar photovoltaic (PV) technology was involves in the SS project, and R & D'of the low cost solar cell materials with high efficiency solar cells were settled as the first 10 years subproject. Considering the two sided nature of the energy strategy, that is, even, in &e period of 1980, continuous growth of mass consumption of the limited fossil ,fuels one side, and becoming severe the global environmental issue on the other side, AIST in MITl in Japan has decided to establish "New Sunshine Program" for the development of clean energy technology and environmental technology. Figure 2 illustrates a comprehensive structure of the new program and its relation to 1he;Sunshine Project which was formulated in May 1973, prior to the first energy crisis, and started in 1974, the Moonlight Project which was initiated in 1978 for the energy saving technological development, and also environmental technology project progressed from 1989[5]. The past injected budgets are also inserted in the figure. While the new program consists of three parts; a) Renewable Energy Development Technology, b) High Efficiency Utilization of Fossil Fuels and Energy Storage, and c) International Energy Cooperation, so-called WENET (World Energy Network) utilization hydrogen fuel production technology by PV and distributions with a wide area energy utilization network system namely as "Eco-energy City".

In the several years from 1965, the band structure parameters of more than ten kinds of new semiconductors were characterized by the modulation spectroscopy, and computerized measurement system on the energy spectra of optical absorption and reflectance were well established in the year period of I970lh. Then next step of my research dream was focused on an attempt to realize a synthetic semiconductor, which has a controllability of band parameters, for example, energy gap Eg. The experimental attempt had been realized by a ternary Si-As-Te amorphous semiconductor in the micro gravity environment by the TT 500 A Rocket [6] and FMPT (First Material Processing Text) in the Space lab J [7]. This Si-As-Te amorphous semiconductor system has various interesting points in views of both basic physics and technological applications. Since the Si-As-Te system consists of mixed combinations of IV-Ill-I1 hedral bonding, it has a large structural flexibility to construct a high possibility of random network, which yields a very large glass formation region with a wide physical constant controllability as shown in Fig. 3. For example, the energy gap can be controlled continuously in the range from 0.6eV to 2.5eV, which covers the energy gaps of conventional crystalline semiconductors; 'Ge (0.66eV), Si (I.OeV), &As (1.43eV) and GaP(2.25eV). Figure 4 shows an effect of Ni doping on the electrical conductivity of Si9As,4Te21. dramatic enhancement of the A electrical conductivity, more than 7 orders of magnitude, is seen for the FMPT material, while an increase of only 3 orders on terrestrial material. Also found is almost zero activation energy for the doped FMPT material, which contrasts highly with a slight decrease (25%) in the activation energy upon doping in the terrestrial material. In both cases, a change in the conduction type from p-type (hole in undoped material) to n-type (electron in Ni doped material) is confirmed by means of thermoelectric power
Si

Fig.3 Eqqui-energv gap confour lines of the Si-As-Te

amorphous semiconductor in the Gibbs friungle.

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3rd World Conference on Photovoltaic Energy Conversion

May 11-18, 2003 Osokn, Japan

d
0.772sv
3

3.1 3.2 3.3 Reciprecal TemwrJIura lrr(rlo3M)

3.A

Fig.4 A comparison of the doping eflciency by Ni doping on both terrestrial and micro gravity (FMPT) made Si-As-Te[7].

measurement. Such large existence of the effect of doping on electrical conductivity has never been observed for melt-quenched chalcogenide glass system. This high doping effiency in the FMPT sample implies either a lower native defect density or a greater doping efficiency of Ni additives. More detailed analyses and theoretical consideration on this item are discussed in OUI previous paper [7]. All the experimental results suggest the realization of homogeneous amorphous network structure with a minimized disorder by the material processing in a micra gravity environment. The material processing in space would contribute largely to the physics of disordered materials as well as to the development of new materials for semiconductor electronics. As has been mentioned above, the valency electron control to the Si-As-Te is quite difficult in principle due to the shuctural flexibility in chalcogenide. In 1975, a beautiful success of valency electron control to amorphous

silicon (a-Si) has been reported by Spear and Lu Comber [SI. AAer ow own preliminally investigations on a-Si 191. we have started a series of basic research such as deposition condition, valency electron control in a-Si, a-SiC and their microcrystallines ( c). I . ! As has been reported elsewhere, a-Si alloys can he deposited onto any inexpensive substrates with low temperamre less than 300C. Moreover, it is possible to form very wide area thin films due to a vapor phase growth onto non-crystalline substrates. Another noticeable property of these a-Si alloys is existence of valency controllahility by doping of substitutional impurity atoms with mixing of impurity gasses such as B2H6 and PHI, etc. Therefore, in view of production sequence, this material system has an excellent massproduceability with large scale merit. Significances of a-Si alloys as the solar cell materials are summarized in Table 1. As the preparation technology for a-Sic alloy, the plasma CVD is now widely utilize every where. While ECR C W and Ion-heam CVD (1s-CVD) are intensively investigated in a recent few years. The unique advantage of the ECR CVD is that the growing surface receives almost no bombardment damages by electrons andor other heavy species soft landing having an energy of several tens of eV [IO]. This effect might result not only in prevention of weak bonds from heiug introduced into the network but also suppression of the diffusion of long lifetime radical species due to the raised surface temperature. It is expected that films with dense network and low defect density are formed. For the deposition of a-SiC and U c-Sic, hydrogen is used as an ECR plasma excitation gas, with a mixture of S i b , CHI and B2H6 or PH, are usually employed as a reaction gas for the growth of p- and n-type SiC:H. Details of the preparation conditions are reported in reference [ll]. Since the operation pressure is in the range of IO and IO4 Torr, the lifetime of chemically active hydrogen radicals are quite long, so that a large amount of hydrogen radicals will reach the growing surface and play an important role in

Toble 1. Significances of a-Si:H alloy as a so/ar cell material

A
a-1) a-2) a-3) a-4) Physical Properties Excellent photoconductivities with high absorption coefficient far sun light Low dark conductivity High structural sensitivity (Valency electron controllability) Wide range of energy gap controllability I.OeV EO MeV a-SiGe - a-Si - a-Sic

B
b-1) b-2) b-3)

Fabrication Technology Wide area thin film (Plasma CVD. ECR, CVD. etc) Low temperature deposition 100C < Ts < 380C p-n control can be accomplished only by mixture gas regulations Can be deposited on any inexpensive substrates

b-4)

<

<

a-5)
a-6)

Easy to make heterojunction (Relatively low interface states) Mechanically strong (because of amorphous network)

b-5)
b-6)

Easy to apply integration technology (HJ. super lattice, tandem cells) Low cost and good massproduceability

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3rd World Conference on Photovoltaic Energy Conversion

May 11-18.2003 Os&, Japan

also on the ratio of hydrogen to reaction gases H2/(Ch+Si&) during deposition. Although the optical energy gap increases with the flow rate of CHa, the effect is not as remarkable as the dependence of hydrogen dilution. Hydrogen dilution has the effect of reducing the hydrogen content in the film, and also of enhancing the degree of microcrystallinity. The formation of Si and Sic micro crystallites are confirmed by Raman spectra as mentioned in the original work [IO]. The Raman spectrum of the films prepared at microwave powers higher than 250 Watts exhibits distinct structures at around 520 and 740 cm?, which correspond to TO phonon'modes crystalline Si and S i c clusters.
4.

R&D EFFORTS T O PRODUCE HIGH EFFICIENCY WITH LOW COST SOLAR CELLS

Fig.5 Dependence o optical energv gaps and dark f conductivitier o p and n- type pc-SiC:H on hydmgen f dilution radio in reaction gosser in ECR CVD [I987 by D.
Knrngom et 01.. reflo]

determining the properties of growing films. Therefore, the dependence of the material properties on the hydrogen dilution ratio in the reaction gas has been investigated. Figure 5 shows the dependence of the optical energy gap and dark conductivity of the samples on the Hz dilution ratio. As the ratio increases, the optical gap (Eo) and also the dark conductivity ( a) of both p- and n-type films , increase. As can be seen from Fig.5, there are two main factors which determine the optical energy gap; one is the composition ratio of Si:CH corresponding to the source gas ratio CHJSih, and the other is the grade of Hz dilution which might be related to the details of the network structure. The film properties are strongly dependent not only on the substrate temperature and microwave power but

The first application to solar cell with a-Si:H has been achieved by RCA group in 1977 with a structure of Schottky barrier type [12]. Since we have concentrated our attention on the valency electron control in a-Si:H, the p-i-n junction type solar cells are fabricated in 1978 [13]. Figure 6 shows a picture of laboratory made solar cells in 1978 including and integrated type high voltage cell which directly applied to Solar Calculator by Sanyo Electric Co. in 1980. With an invention of a-Sic by the author's group in 1980, an 8% efficiency barrier, which was proposed by the photovoltaic system as the feasibility line for the power application, had been broken through as 8.25% obtained in 1981 and become 9.39% in 1983 as shown in Fig.6 [14]. With a-Si:H solar cell, 13.2% efficiency was reported by Mitsui Chemical in 1993. In 1979 another new concept to improve a-Si:H solar cell efficiency has been proposed by the author's group [IS], that is, a multi-band gap stacked solar cell. A series of

Fig.6 Laboratory-made early stage a-Si:H solar cells [I978 by H. Okamoto, I Nitta, and I Hamahwa, rex151 : :

AZO

3rd World Con/erence on Photovoltaic Energy Conversion

May 11-18.2003 Osoka. Japan

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Fig. 7 Phoiovoltoieper/*~~ances. junction stmcfure ondj:V choraeterisrics o/a-SiC/cl-Si heierojuncrion Solor cells (U) and 0). cornporing with tho1 o/ordinoq 0-Si homojunction solar . . cell (c). , , .
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systematic investigations was initiated on. the optimum design theory with selections of material combinations [16]. It has been suggested from the result that the structure of a-Si:W/poly-Si is the .best combination., For the , two, -terminal a-Si;H solar cell stacked with poly-Si [Ill, .a conversion efficiency ,of 15.04% with Voc=1.478V, lsc=16.17mAicm2 and FF=63% has,'beeh obtained under A M I illumination: Figure 8,shows the structure and an . . example of output characteristics of a proto-type 4-terminal stacked cell having 21% efficiency [17]. Along with this concept, wide 'varieties of experimental trials are in progress on the multi-band gap stacked solar cells. For' example, on large area (1200 cm*) a-Si:W a-Si:H attacked solar cells, the efficiency of 10% is reported by Fuji Electric [18]. Recently, the band profiling design study by computer simulation has also been made as an optimum design of the ambipolar carrier transport in' i-layer of the multi band'gap junction.'As an 'experimental trial of, the band profiling shldy a-SiC:H/ a-Si:W a-SiGe:H triple band
,

gaptandem solar cell has been made by Sharp group, and an initial conversion efficiency of 12.4% has been achieved ~191. . . Another important idea to realize the'next generation solar cell is continuous ail plasma CVD production system, notonlythe a-Si:H top cell but also JL c-Si the bottom cell.. A tremendous R & D effort has been inprogress. Figure 9 , . . shows an example ,of recent top data reported by k m e k a , (Kaneka'hchi Chemical Industry) group 14.7% efficiency for R.& D .lcm2 cell area [20], and also 11.6% efficiency for'large area mass production module [20]. Canon has also reported l4:49% for R & D small cell and 13.37% for mass production module with a-SGp c-Si/i c-Si three tandem s&ictuk cell [ZI]. Kaneka has ,recently started the, mpss: production of, this structure solar cell module with a production scale of ZOMWiyear in 2003.
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5.

NEW STRATEGY AND KEY ISSUES FOR PV . . .,. . INDUSTRIALIZATION

In spite of various advantages in photovoltaic.power generation as.mentioned above, a big barrier impeding the . ,

Fir. 8 Cell shuchlre (a) and V-Icharacteristics (6) of a-Si:H//poly-Si 4 terminol stacked solar cell by Osaka Universi?, [U]

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3rd World Conference on Phorovolroic Energy Conversion

May 11-18.2003 Osokn. Japan

expansion of large-scale power source application was the high price of solar cell module, which was more than $30/Wp (peak watts) in 1974. Therefore, the cost reduction of the solar cell is of prime importance. To achieve this objective, tremendous R&D efforts have been made in a wide variety of technical fields, from solar cell material, device smcture, and mass production processes to photovoltaic systems over the past 20 years. As a result of recent. fifteen years R&D efforts, about one order of magnitude price decrease has been achieved, and now come down less than $ 4 N p in a firm hid for the large scale purchase. In December 1994, a new initiative of Japanese domestic renewable energy strategy, so called. Fundamental Principles to Promote New Energy Developments and Utilization has been identified by the Cabinet Meeting. Related action planning by law such as tax reduction, government subsidy etc. are approved by the Congress on April IO, 1997. The strategies are applied to not only whole ministries and government offices but also local g o v e m e n t authorities and private enterprises. With this government new policy, development and promotion of PV technologies have been complied as the most promised project. An integrated installation volume of 4OOMWp PV modules by FY2000 and 4.82CWp by FY2010 for Japanese domestic use are scheduled as a mile stone in the program. A special regulation of tax reduction for investment to the renewable energy plant, a government financial support of 1/2 subsidy on the PV system for public facilities so called PV Field Test Experiments, 113 subsidy for the private solar houses as the PV House Planning of the field testing etc., are in progress. Number of government subsidy accepted PV house increases

300

I Progress

of PV Module Productton tn Japan

11 4
2 0

._

200

Utility Power Use Consumer Aoolication

95

96

97

98

99

00

01

02

Calendar Year
Fig. I O Annual Pmducrions ofsolar Cell Module.

doubling year by year. On the other hand, in the PV Field Test Experiment totals of 259 sites with 6.84 M W has been installed during 7 years. As the result of accelerated promotion strategy, in fact, sales price for the 3kW solar photovoltaic system for private house decreases very sharply about one third for example, from 2MTkW in 94 down ti 0.72 M W W in 02. Figure 10 shows transitions of the solar cell module annual production in Japan since 1995 as surveyed by Paul Maycwk [221. As can be seen from the figure, a remarkable increase of the annual production has been seen since starting of the New Sunshine Project in 1993. Let us embark on a new energy revolution with clean-energy photovoltaics. Might it be possible to accomplish the clean-energy revolution within the next 25 years? It would be a worthy challenge, no longer simply a fanciful dream.
0

REFERENCES
[ 111 international C a n t on Modulation Speetrorcopy, University of

[ I l l W. Ma, T. Horiuchi, M. Yorhimi, K. Hanari, H. Okamoto. Y.

Hamakawa, h o c . PVSEC-6 (New Delhi, 1992) p. 463. [12]D. E. Carlson and C. R. Wronrki: Appl. Phys. Len.28.671 (1977) (131H. Okamoto, Y. Nina. T. Adachi and Y. Hamakawa, Surface Science86(1979)pp. 486-491. [I41 Y. Hamakawa. K. Fujimoto, S. Nonomura and H. Okamoto: New
types of high efficiency solar cell based on a-Si Appl. Phys. Len. 43

Arizona, Tucson, Arizona (Nov.1970) [Ilsee far example, Y. Hamakawa and T. Nishino: Reccnt advancer in modulation spec~oscopyChspt.6 of Optical Pmpenics of Solids New Developments, Ed. by B. 0. Seraphin, N o h Holland Pub. Co. (1976) pp.255-353 PIA. B. Meincl: Physics Today (1972) p.44 and many othm. 14lY. Hamakawa: A New Role o f Semiconductor Technology Challenges O Efficient Solar Energy Utilizations 1. EIeermnic I
~

(1983) pp.644-646. [ISIY. Hamakawa. H. Okamoto and Y. Nina: Appl. Phyr. Len.35, IS (1979) and Japanese Patent Sho-54-32993 and U.S. Patent 4,271.328. March 20, 1979. [16]H. Takakura, Jpn. J.Appl. Phys.31 (1992) 2394.
[17]W. Ma, T. Honuchi,

Moreriols (1974) pp.524-529. I1ibld (1974) pp.530-534.

[SIK. Miyarawa, K. Kato, K. Kawamura: Repan of Solar Energy Division Meting, Technology & Industrial Council, MlTI March (1997)pp. 1-8. [6]Y. Hamakawua: Ceramics, 22 (1987) p. 277. [in Japanese]

C.C. Lim, M. Yoshimi. H. Okamota and Y.

Hamakawa. Roe. 23d IEEE PVSC, 1993, p.338.

. [7] Y. Hamakawa. W Shams-Kolahi, K. Hanori, C. Sada and H.

Okamoto: Journal ofApplied Microgravity vol. I2 (1995) pp. 27-37.

[18]V.IchikawaandH.Sakai,Pmc. IWCPEC,Hawaii(1994)p.441 [19]Y. Nakata, S. Monguchi, Y.Inoue, K. Nomoto, A. Yokota, M. ltoh

and T. Truji: Optoslectronics- Devices andTechnol. (1990)-5,209 [20]K. Yamamoto and Y. Tawada. Tech. Dig. WCPEC-111to be reponed (2003) S20-B9-03 and 5PL-DI-03. [21] K. Saito and K. Ogawa: to be reponed in WCPEC-Ill (2003) 50-D14-04.

181W. E.Spear and P. G LeComber, Philos. Mag. 33 (1976) 935.

191 H. Okamoto, Y.Nina, T. Adachi and Y. Hamakawa, Surf Sei. 86 (1979) 486.
[ I O ] Y. Hamakawa, Y Malsumoto, G Hiram and H. Okamoto, MUS .

Symposium 164(1991)pp.823-829.

[22] Paul Maycock PV NEWS vol. 22, No.5 May (2003) pp. 1-3.

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