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ThinFilmMicrobatteriesPreparedbyPulsedLaserDeposition

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Journal of the Korean Physical Society, Vol. 51, No. 3, September 2007, pp. 1055∼1062

Thin Film Microbatteries Prepared by Pulsed Laser Deposition

Hui Xia

Advanced Materials for Micro- and Nano-System, Singapore-MIT Alliance, Singapore

S. B. Tang

Department of Mechanical Engineering, National University of Singapore, Singapore

Li Lu∗

Advanced Materials for Micro- and Nano-System, Singapore-MIT Alliance andDepartment of Mechanical Engineering, National University of Singapore, Singapore

(Received 13 November 2006)

There is a growing interest in thin film microbatteries due to miniaturization of electronic devices.The reduction in current and power consumptions of electronic devices makes microbatteries possibleas power sources. Hence, if micro-scale thin-film batteries are to be developed, a suitable fabricationprocessing technique for thin-film cathodes, anodes and electrolytes becomes crucial. Among variousthin film deposition techniques, pulsed laser deposition (PLD) is a relatively flexible and powerfultechnique for preparing high quality and dense thin-film electrodes on a laboratory scale. Thispaper reviews recent developments in the fabrication of thin-film electrodes by using PLD.

PACS numbers:Keywords: Thin-film microbatteries, Pulsed laser deposition, LiCoO2, Amorphous Si, Thin film electrolyte

I. INTRODUCTION

There is a growing interest in fabrication of recharge-able lithium-ion batteries in microscale dimension. Inrecent years, miniaturization of electronic devices forvarious applications has required very low current andpower consumption, which has made it possible to usethin film microbatteries (TFBs) as power sources forthe microelectronics systems, such as complementarymetal oxide semiconductor (CMOS) memory chips, mi-croelectromechanical systems (MEMS), smart cards, im-plantable medical devices, etc. If TFBs-based energystorage devices are to be realized, three processes in thefabrication are essential: (1) preparation of a thin-filmcathode on a current collector, (2) preparation of a solidelectrolyte film, and (3) preparation of a thin-film anode.It is especially important to develop a high-quality thinfilm cathode with high energy density, good reversibil-ity, stable voltage, and low cost. LiCoO2 is the mostcommonly used cathode material for lithium-ion batter-ies due to its high capacity, high operating voltage andlong cycle-life [1–3]. Therefore, LiCoO2 thin film cath-odes have been intensively studied for microbatteries. Asfor the electrolyte film, lithium phosphorus oxynitride(LiPON) was first reported by Bates et al. [4] and is now

∗E-mail: mpeluli@nus.edu.sg

widely used as the Li electrolyte in thin-film lithium-ionbatteries. Due to the low melting point of the lithiummetal and its strong reactivity with air and moisture,a new thin-film anode, such as an amorphous Si thinfilm anode [5], has been developed to replace the lithiumthin-film anode in microbatteries.

If the fabrication of thin-film microbatteries is to berealized, appropriate fabrication methods leading to ex-cellent microstructural and compositional control in thethin-film electrodes are important. Various depositionmethods have been successfully applied for fabricatingthin-film electrodes, such as radio frequency (rf) sputter-ing [4,6,7], pulsed laser deposition (PLD) [8–10], chemicalvapor deposition (CVD) [11], spin coating [12] and elec-trostatic spray deposition [13] etc. Among these tech-niques, PLD is one of the methods widely recognized asa very promising, versatile and efficient method in thegrowth of high quality films from a variety of materi-als even material containing volatile components withcomplex stoichiometry, on a laboratory scale. For thisreason, it is well suited for the growth of transitionalmetal-oxide thin-films compared with other conventionalevaporation techniques where lithium loss occurs due tovolatilization.

In this paper, recent developments in the fabricationof thin-film electrodes for microbatteries by using PLDare reviewed. Because of its being an important cath-ode material, the surface morphology, the microstructure

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Table 1. Crystallization temperatures for LiCoO2 thin-film prepared by different techniques.

Deposition Chemical vapor Electrostatic spray

TechniquePLD Sputtering

deposition depositionSpin-coating

LiCoO2 thin-film

crystallization300 – 600 ◦C 700 – 800 ◦C 700 ◦C 600 – 800 ◦C 800 ◦C

In situ heating, In situ heating, In situ heating,Annealing In situ heating

post-annealing post-annealing post-annealingPost-annealing

Reference [7–9] [4,6,7] [11] [13] [12]

Fig. 1. Schematic illustration of a pulsed laser depositionsetup.

and the electrochemical properties of LiCoO2 thin-filmelectrodes prepared by using PLD are presented. Theamorphous Si thin-film anode coupled with a LiCoO2

thin-film cathode, and the electrochemical properties ofthe full cell are presented. Finally the possibility of fab-ricating all-solid-state thin-film batteries by using PLDis discussed.

II. THE PULSED LASER DEPOSITIONPROCESS

A schematic illustration of a typical PLD system isshown in Figure 1 [14]. Normally, a PLD system consistsof a multi-target holder and a substrate holder with aheater attached in a vacuum chamber. Thin-films of thedesired materials and compositions are deposited ontothe heated substrate by the ablation of a material froma rotating solid target surface, normally by using a sin-gle short laser pulse. Typically, an ultra violet excimerlaser, such as ArF, KrF and XeCl at wavelengths of 193,248 and 308 nm, respectively and with a pulse widthof tens of nanoseconds or shorter, is employed. Othertypes of lasers, for example, the YAG laser, have alsobeen demonstrated to be effective. A set of optical com-ponents is used to focus the laser beam to the target.Film growth can be carried out in a reactive environ-ment containing any kind of gas with or without plasmaexcitation at a target-to-substrate distance of about 2 –10 cm.

The PLD process can be typically divided into fourstages: (1) laser radiation interaction with the target, (2)the formation of a plasma plume and transport towardsthe substrate, (3) interaction of the ablated species withthe substrate, and (4) nucleation and growth of a thin-film on the surface of the substrate [15]. When the laserradiation is absorbed by a solid surface, electro-magneticenergy is converted first into electronic excitation andthen into thermal, chemical, and even mechanical en-ergy to cause evaporation, ablation, plasma formation,and exfoliation. Evaporants form a ‘plume’ containing amixture of atoms, molecules, electrons, ions, clusters andmicron-sized solid particulates and rapidly expand intothe vacuum with a narrow forward angular distribution.The ablated species have high kinetic energy of typicallylarger than 30 eV and high initial velocities higher than106 cm/s [16]. The kinetic and the internal excitationenergies of the ablated species can also be used to assistfilm formation and to promote chemical reactions.

III. LiCoO2 THIN-FILM CATHODE

1. Microstructure and Morphology

The formation of a layered structure for a LiCoO2

cathode is known to be essential. Therefore, the LiCoO2

thin-film must be well crystallized. If the crystallinity ofthin-film cathodes to be ensured, sometimes annealing isneeded after deposition. However, high temperature an-nealing is likely to damage substrate materials includingunder layers. In addition, thermal annealing may inducemicrocracks in the cathode films, which lead to failure inthe subsequent deposition step due to the nonuniformityof the solid electrolyte film on the cathode. Therefore,it would be beneficial if a crystallized LiCoO2 thin-filmcathode could be directly deposited without further an-nealing. One of the effective methods is through energydelivered to the growing film by substrate heating or ionbombardment. With in-situ substrate heating, PLD cangrow well-crystallized films without any post-annealingprocess. In addition, the crystallization temperature forthe film can be lowered due to the high kinetic energyof the adatoms when using PLD. As Table 1 shown, the

Thin Film Microbatteries Prepared by Pulsed Laser Deposition – Hui Xia et al. -1057-

Fig. 2. SEM micrographs of LiCoO2 thin-films preparedby PLD [10], and Sputtering [4].

PLD technique shows the lowest crystallization temper-ature for LiCoO2 thin-films. As Julien et al.reported[8], well-crystallized and single phase LiCoO2 thin-filmscan be prepared at a substrate temperature as low as300 ◦C. Since the PLD technique is able to prepare well-crystallized thin-films at relatively lower temperaturesthrough in-situ substrate heating, high-quality thin-filmswith high densities and smooth surfaces without cracksare expected.

Figure 2 shows the SEM images of the LiCoO2 thin-films deposited on Si substrates by using PLD [10] andsputtering [4]. The LiCoO2 film deposited by using PLDis composed of well-defined grains and exhibits a smoothsurface without any pinholes or cracks while the LiCoO2

film prepared by sputtering and annealing is composed ofsmaller grains and exhibits a wide crack, probably causedby thermal shrinkage after post-annealing. Though thesputtered LiCoO2 film was annealed in air at 700 ◦C, thegrain size of the film is much smaller than that of thefilm deposited by using PLD at a substrate temperatureof 600 ◦C. It is clear that PLD can really reduce thecrystallization temperature of deposition for the LiCoO2

thin-films compared with that for sputtering technique.Although the compositions of the thin-films deposited

by using PLD are normally close to those of the tar-gets, that is not always the case when the targets containvolatile elements and/or have high vapor pressures [17].In the case of lithium-containing materials, the content oflithium in the resultant thin-films tends to be lower thanthat in the targets. Li deficiency in the film may leadto structural changes and to the formation of impurities,which will directly affect the electrochemical activity of

Fig. 3. XRD spectra of (a) LiCoO2 thin-film depositedfrom a target without Li2O and (b) LiCoO2 thin-film de-posited from a target with 15 % Li2O [8].

the film. In order to compensate for the loss of lithiumduring depositions, one has to add an excess content ofLi2O to the targets. Figure 3 (a) and (b) show XRDspectra of the films deposited using the stoichiometricLiCoO2 target and the LiCoO2 target with 15 %w Li2O[8]. It can be seen that the LiCoO2 film grown from thestoichiometric target without any excess Li2O shows thepresence of the a cobalt-oxide Co3O4 impurity while theof Co3O4 impurity completely disappears and the filmshows a layered structure when the target is incorpo-rated with 15 % excess Li2O.

In addition to the crystallinity and the surface mor-phology, the textures of the LiCoO2 films will alsostrongly affect the electrochemical activity. In the PLDprocess, the high degree supersaturation of an ablatedflux makes 2D heterogeneous nucleation of thin-filmspossible [15]. This 2D-nucleation is favorable for thelayer growth mode of the films. Hence, highly ori-ented or even epitaxial thin-films can be easily obtained.For a thin LiCoO2 film, it is easy to form a preferred(003) orientation due to the lowest surface energy forthe (003) plane. For a thick LiCoO2 film, it will formpreferred (101) and (104) textures due to a minimiza-tion of the strain energy. The electrochemical lithiumintercalation/de-intercalaltion behavior in LiCoO2 thinfilms depends strongly on the orientation of the grains.

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Fig. 4. XRD spectra of (a) LiCoO2 thin-film with a pre-ferred (003) texture and (b) LiCoO2 thin-film with a preferred(104) texture.

Grains with their (003) plane parallel to the substratewill block the flow of lithium ions whereas grains withtheir (101) and (104) planes parallel to the substrate willfacilitate diffusion of lithium ions. If higher electrochem-ical activity and capacity is to be achieved, it is pref-erential to grow the film with (101) and (104) textures.There are two methods to control the texture of the films.The first one is to grow a thick film for developing thepreferred (101) and (104) textures, and the second oneis to use a textured substrate to induce the (101) andthe (104) textures of the film. Iriyama et al. [9] suc-cessfully prepared preferred (003) textured LiCoO2 filmsand randomly orientated LiCoO2 films by using PLD fordifferent deposition durations. It was found that the tex-ture was developed by an increase in the strain energywith increasing thin-film thickness. We also successfullyprepared the (003) textured and (104) textured LiCoO2

thin-films on Pt/Ti/SiO2 (amorphous)/Si and Au/MgO(textured)/Si substrate, respectively [18]. Figure 4 showsthe XRD spectra of the two textured films. The differ-ent textures of the LiCoO2 films were induced by usingthe substrate orientations. Therefore, the textures of theLiCoO2 thin-film can be controlled by using different tex-tured substrates and processing parameters.

2. Electrochemical Properties

The electrochemical properties of the LiCoO2 thin-films are highly dependent on the microstructure, thesurface morphology, and the purity of the films. Thewell-crystallized LiCoO2 thin-films with layered struc-ture, smooth surface and high purity can provide bet-ter electrochemical properties. Figure 5(a) shows thetypical charge/discharge curves of the LiCoO2 thin-filmelectrode deposited using PLD. As Figure 5(a) shown,the charge/discharge curves exhibit five voltage plateaus

Fig. 5. (a) Charge/discharge curves of the Li/LiCoO2 cellwith thin-film LiCoO2 cathode (b) The differential capacityvs. voltage for the Li/LiCoO2 cell. (3 – 4.7 V, current 15µA/cm2).

for both the charge and the discharge processes. Thelarge 3.9-V plateau corresponds to the first-order metal-insulator transition [19,20], and the two minor plateauscorrespond to order/disorder transitions [21,22] near thecomposition Li0.5CoO2. Another two plateaus above 4.5V are also observed, which agrees with Chen, Lu andDahn’s observation [23] on LiCoO2 composite electrodes.These two plateaus are attributed to the phase transi-tions from the O3 phase to the H1-3 phase and from theH1-3 phase to the O1 phase [23], as predicted by Vander Ven et al. [24]. Figure 5(b) shows the dQ/dV curvesderived from the charge/discharge curves in Figure 5(a),where the peaks in the dQ/dV curves correspond to thevoltage plateaus in the charge/discharge curves. FromFigure 5(b), it is obvious to see that the differential of thecapacity becomes zero at 4.7 V, indicating full delithia-tion from the LiCoO2 film at 4.7 V. The well definedvoltage plateaus and the small irreversible capacity be-tween charge and discharge, even when charged to 4.7V, indicate good crystallinity of the film with a layeredstructure.

Thin Film Microbatteries Prepared by Pulsed Laser Deposition – Hui Xia et al. -1059-

Table 2. Li ion conductivity and electron conductivity of the Li electrolyte thin-films prepared by PLD.

Electrolyte thin-film Lithium phosphorus Li3.4V0.6Si0.4O4 Li3.25Ge0.25P0.75S4 Li0.5La0.5TiO3

by PLD oxynitride (LiPON) (LVSO) (Thio-LISICON) (LLTO)

Li ion conductivity (σ) S/cm 1.6 × 10−6 2.5 × 10−7 2.2 × 10−3 2.2 × 10−5

Electron conductivity (σ) S/cm - 7.4 × 10−13 1.5 × 10−7 3.5 × 10−11

Reference [34] [35] [36] [37]

Fig. 6. The differential capacity vs. voltage for theLi/LiCoO2 cell using (a) (003) textured LiCoO2 thin-filmcathode and (b) (104) textured LiCoO2 thin-film cathode[18].

As we discussed above, the texture of the LiCoO2 thin-film affects its electrochemical properties. Figure 6 showsthe incremental capacity, dQ/dV , obtained from the firstcharge/discharge curves of both LiCoO2 films with pre-ferred (003) and (104) textures [18]. The dQ/dV curvesof the LiCoO2 films with both the preferred (003) and(104) textures show three pairs of peaks. One pair of ma-jor peaks is around 3.9 V, and another two pairs of minorpeaks are around 4.1 and 4.2 V, corresponding to thethree pairs of voltage plateaus in the charge/dischargecurves. Comparing Figure 6(a) with Figure 6(b), we

can see that the LiCoO2 film with a (104) texture hasa smaller peak separation (10 mV) between the anodicand the cathodic peak than that (20 mV) of the LiCoO2

film with a (003) texture. The polarization of the cellis induced by the cell resistance, which is mainly con-tributed by the lithium ion transport into and throughthe electrode. Therefore, these results suggest that thediffusion and the migration of Li ions are faster in theLiCoO2 film with a preferred (104) texture than in theLiCoO2 film with a preferred (003) texture.

IV. AMORPHOUS Si THIN-FILM ANODE

1. PLD Amorphous Si thin-film Anode

The major drawback of Li microbatteries is the lowmelting point of Li metal and its strong reactivity withmoisture and oxygen, which limits its application to be-ing integrated into circuits. Therefore, other anode ma-terials must be investigated to replace the lithium thin-film anode for the all-solid-state thin-film lithium-ionbatteries. Recently, the amorphous Si material has beenstudied as an anode material for lithium-ion batteries.Si is recognized as a high-potential alternative anodematerial because Si has a maximum theoretical capac-ity of 4000 mAh/g in the form of Li21Si5. The advan-tage of amorphous is claimed elimination of the inter-face between two phases with different lithium concen-tration, leading to homogeneous volume expansions andimproved cycling behavior [25,26]. So far, amorphous Sithin-film anodes have successfully been prepared by us-ing chemical vapor deposition (CVD) [5], radio-frequency(r.f.) magnetron sputtering [27,28] and vacuum evapo-ration [29–31]. In our lab, we successfully fabricated anamorphous Si thin-film anode by using PLD.

Figure 7 shows the first 10 cycles for thecharge/discharge curves of an amorphous Si (a-Si) thin-film anode measured between 0.01 and 1.5 V versusLi/Li+ at a current density of 100 µAcm−2 [32]. Duringthe first discharge, the potential rapidly dropped to 0.5V and stayed at a small plateau near 0.5 V, and thengradually dropped to 0.01 V, which could be caused bythe formation of a solid electrolyte interface (SEI) layeron the film electrode surface, arising from the liquid elec-trolyte decomposition reaction [33]. For subsequent cy-cles, no such plateau was observed during the discharge.The first discharge and charge capacities are, respec-tively, about 105 µAh/cm2 and 64 µAh/cm2 with an

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Fig. 7. The first 10 charge/discharge curves of for the Lia-Si cell with a-Si thin-film electrode (0.01 – 1.5 V, current 100µA/cm2) [32].

irreversible capacity loss of about 40 %. Other than thefirst cycle, the charge and the discharge capacities in thesubsequent cycles are highly reversible and a reversiblecapacity of about 64 µAh/cm2 is maintained.

2. LiCoO2 thin-film cathode//amorphous Sithin film anode - full cell

A LiCoO2//liquid electrolyte//a-Si full-cell with a 500nm LiCoO2 thin-film on a SS substrate as a cathode wascharacterized. Twenty charge-discharge cycles between1 and 4 V at a constant current density of 20 µA/cm2

are shown in Figure 8(a). The first charge curve is alittle different from the subsequent ones. The capacityof the first charge is much larger than that of subse-quent charges due to the irreversible capacity loss of a-Si film and the LiCoO2 film for the first cycle. Fromthe charge/discharge voltage profiles, it is noted thatthe full cell could be operated in the potential rangebetween 3 and 4 V without a voltage plateau region.The charge/discharge capacities as a function of the cyclenumber are shown in Figure 8(b). Though the coulombicefficiency was very low at the first cycle, it was improvedduring following cycles and reached 83 % at the 20th

cycle. For these 20 cycles, the discharge capacity wasretained at about 20 µAh/cm2, and almost no dischargecapacity fade was observed, exhibiting good capacity re-tention.

V. ALL SOLID-STATE THIN-FILMMICROBATTERIES BY PLD

PLD is not only a powerful tool to prepare thin-filmcathodes and thin-film anodes for microbatteries, it isalso a flexible technique to prepare solid Li electrolyte

Fig. 8. (a) Charge/discharge curves for LiCoO2/Liquidelectrolytea-Si full cell at a constant current density of 20µAcm−2 between 1 and 4 V, and (b) charge/discharge capac-ities vs. cycle number.

thin films for microbatteries. Tabel 2 lists various Lielectrolyte thin films prepared by using PLD. The Li-ion conductivity of different electrolyte films ranges from10−3 to 10−7 S/cm while the electron conductivity rangesfrom 10−7 to 10−13 S/cm [34–37]. These electrolytethin-films with high Li ion conductivity and low elec-tron conductivity are promising for their applications asLi electrolyte films for microbatteries. Therefore, withsequential PLD method, all solid-state thin-film micro-batteries can be fabricated. Kuwata et al. [35] fabri-cated thin-film microbatteries consisting of LVSO solidelectrolyte, crystalline LiCoO2 cathode, and amorphousSnO anode. All the thin-films were prepared by usingPLD. A schematic cross-sectional view of their thin-filmmicrobattery is shown in Figure 9(a) [35]. The batteriestypically have an area of about 0.23 cm2 and are about2-µm thick. This thin-film battery cycled between 0.7and 3 V had an initial discharge capacity of about 9.5Ah/cm2 and could retain 45 % of its initial discharge ca-pacity after 100 cycles. Figure 9(b) shows the dischargecurves of this thin-film battery at different current rates

Thin Film Microbatteries Prepared by Pulsed Laser Deposition – Hui Xia et al. -1061-

Fig. 9. (a) Schematic cross-sectional view of a thin-filmlithium-ion battery, (b) Discharge curves at different currentdensities for a thin-film lithium-ion battery at room temper-ature [35].

[35]. It is obvious to see the potential drop as the cur-rent increases. Due to the high Li ion conductivity ofthe electrolyte, the ohmic drop from the electrolyte isnegligible and the huge ohmic drop observed is probablydue to the interface resistance.

VI. CONCLUSIONS

PLD is a powerful and flexible tool for producing high-quality thin-film electrodes and thin-film electrolytes formicrobatteries. With PLD, the crystallized temperaturefor LiCoO2 thin films could be lowered and high-puritysingle phase LiCoO2 films could be prepared and the tex-ture of the film could be controlled. With PLD, an amor-phous Si anode can be easily prepared and successfullycoupled with a LiCoO2 thin-film cathode to compose thefull cell. Different kinds of Li electrolyte thin-film can beprepared by using PLD with high Li ion conductivity andlow electron conductivity. A sequential PLD technique,it is promising for making reliable thin-film microbatter-ies.

ACKNOWLEDGMENTS

This research was supported by Advanced Materialsfor Micro- and Nano- System (AMM&NS) programmeunder the Singapore-MIT Alliance (SMA) and by theNational University of Singapore.

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