A combinatorial synthesis system consisting of co-sputtering multiple radio frequency (RF) cathodes was developed to investigate the presence of new amorphous solid electrolytes in a pseudo-ternary Li3PO4-Li4SiO4-LiAlO2 system. Oxynitride solid-electrolyte films were synthesized under an N2 atmosphere by reactive RF sputtering with cathodes made of different materials, such as Li3PO4, Li4SiO4, and LiAlO2 installed at different positions in the chamber. The formation of amorphous films with no grains and a continuous atomic distribution was confirmed using scanning electron microscopy and energy-dispersive X-ray spectroscopy. In a single synthesis, we fabricated an oxynitride solid-electrolyte film, in which the composition range of the components was approximately one-eighth that in the corresponding pseudo-ternary system. The highest Li-ion conductivity of 3.1 × 10−6 S cm−1 was obtained for the LiPSiAlON film with a composition ratio of LiPON : LiSiON : LiAlON = 48.5 : 33.9 : 17.6. The different bonding states of O and N in the LiPSiAlON film doped with P, Si, and Al were examined using X-ray photoemission spectroscopy. The ionic conductivity was improved by the mixed anion effect. The combinatorial synthesis enables the efficient optimization of the chemical composition and facilitates the development of highly conductive amorphous solid electrolytes.

We have successfully developed a mass-productive sputtering module for insulating materials and advanced PbZrTiO3 (PZT) process technology which enable low temperature crystallization of PZT (<500 deg.C) and achieve higher piezoelectric coefficient and breakdown voltage of PZT films

In recent years, discussion on power consumption and latency of GPU used for Al application has started. In order to realize further highspeed processing and low power consumption of the GPU processing a huge amount of data, it is necessary to consider the packaging structure of the GPU [1]. The current GPU package structure is based on the package substrate using flip chip PoP (Package on Package) technology and Si interposer. In this structure applied, the wiring distance is increased due to the structural restriction of signal transmission through the Si interposer on the package substrate, which is the cause of the increase in power consumption and latency. Therefore, the packaging structure around the Si interposer has been focused, and expected structures that does not use the Si interposer have been proposed [2]. A method of directly forming fine wiring layers which plays a role of RDL (Redistributed Layer) by using a photosensitive insulation material on a build-up substrate without using a Si interposer has been reported [3]. Furthermore, in view of the high frequency trend of the signal frequency, the development of glass-epoxy materials having low D-f (dielectric loss constant) and low D-k (dielectric constant) material properties as a build-up film is proceeding [4]. It is expected that it will be a more effective method to effectively utilize the characteristics of low D-f and low D-k and to form fine wiring on the build-up layer using semiconductor fine wiring technology. For future high density packaging, plasma dry etching technology aiming fabrication of multilayer wiring on build-up film has been developed [5]. In this paper, the results of microfabrication of build-up thickness of 5 mu m are reported for the purpose of fabricating fine wiring on build-up film using dry process. This technology has been developed as one of new SiP (System in Package) technologies for realizing future heterogeneous integration. The process results of dry etching and Cu electroplating are described. In order to adapt to chip mounting, the size of the wiring formed in the build-up layer is targeted at line / space = 2 mu m / 2 mu m. The reason for using Si substrate instead of mold panel is because it is suitable for use of expensive NGD (known good die). In Si semiconductor packaging, very stable technology corresponding to Si substrate of 300 mm size has been established up to today. And, for Cu fine wiring formation on a build-up film using a dry process, it is also necessary to ensure sufficient adhesion between the Cu seed layer and the build-up film. In order to manufacture highly reliable fine Cu wiring, it is necessary to evaluate the controllability of good adhesion of the seed Cu layer / glass epoxy film interface. Fluorine compound gas is used for dry etching of buildup film. There are residues containing fluorine on the surface to be etched. These residual fluorine compounds reduce the adhesion between the build-up film and the seed layer for Cu plating. Therefore, it is necessary to construct a method of dry process to improve the adhesion to the seed layer by eliminating the effect of residual fluorine compound. The change in the surface free energy before the seed sputtering process is compared with the peel test result of the Cu seed layer. Basic investigation results on the surface condition of the build-up film and the adhesion of the seed film are reported.

All-solid-state thin-film secondary battery (TFB) has come to recognized as one of the key enabling technologies for stand-alone MEMS/sensor devices which are indispensable for internet-of-things (IoT) solution. This paper presents on anode material development for TFB. Silicon is promising candidate to replace metallic lithium due to high heat-resistant and even high theoretical specific capacity. In this work, the effect of titanium addition on sputtered silicon electrode performance was investigated in order to improve not only mechanical damage but also resistivity.

Thin-film batteries (TFBs) are produced by thin-film deposition technology which has special advantages that are not only intrinsically safe as their being all-solid-state but also thin, small, lightweight, and flexible [1], and also have the features such as low self-discharge and long cycle-life. As MEMS and high-density packaging technology grows, the device size becomes smaller and there is a growing demand for miniaturized devices with stand-alone power supply supported by TFBs and energy harvesting devices [2, 3]. However, Li metal that is commonly used as anode in TFBs, has low melting point as around 180 deg.C and cannot be employed for packaging process that include solder reflow, epoxy molding, and even through-silicon via (TSV). Si is promising anode material due to high specific capacity and low electrode potential, but there are the issuers such as low resistance and electrode breakage due to drastic volume change during cycles. In our previous work, TFBs with high-temperature tolerance was fabricated by all sputtering; Pt/Ti as cathode current collector, 3μm-thick-LiCoO2 with post-annealed at around 600 deg.C as cathode, 2 μm-thick-LiPON as solid electrolyte, 600 nm-thick-Si1-xTix (x=0, 0.03, and 0.12) as anode, and Ni as anode current collector [4], and finally completed by encapsulation with UV curable resin and inorganic lid. The active area of fabricated TFBs was 1.4 mm2. Ti which is inactive material against Li, was used as dopant for not only mitigating mechanical stress but also decreasing resistivity. Cycling was performed between 2.5 and 4.1 V with standard current rate condition, and cycle performance resulted well during 100 cycles. In this work, microstructure of Si-Ti alloy film was adjusted by changing sputtering condition such as process pressure and gas species. Figure 1 shows cross-sectional SEM image of each Si1-xTix films. The effect of Si1-xTix anode microstructure on electrochemical and cycle performance of full cell will be discussed. References [1] T. Jimbo, P. Kim, and K. Suu, Production technology for thin-film lithium secondary battery, Energy Procedia, 14, 1574-1579 (2012). [2] M. Fojtik, D. Kim, G. Chen, Y. S. Lin, D. Fick, J. Park, M. Seok, M. T. Chen, Z. Foo, D. Blaauw, and D. Sylverster, A millimeter-scale energy-autonomous sensor system with stacked battery and solor cells, IEEE Journal of Solid-State Circuits, 48 (no. 3), 801-813 (2013). [3] T. Kuriyama, A. Suzuki, Y. Okamoto, I. Kimura, Y. Morikawa, and Y. Mita, A micromachined all-solid on-chip thin-film battery towards uninterruptible photovoltaic cells, 2018 Symposium on Design, Test, Integration and Packaging of MEMS and MOEMS (DTIP), 153-156 (2018). [4] A. Suzuki, S. Sasaki, and T. Jimbo, Development of All-solid-state Thin-film Secondary Battery for MEMS and IoT Device, The 18th International Conference on PowerMEMS 2018, Proceedings, T5A-03 (2018). Figure 1

Smart ICT (Information and Communication Technology) such as “Big Data”, “Cloud computing” and Smart Functionalities such as Stand-alone Self-activating MEMS/Sensors construct Smart Systems which enable IoT (Internet of Things), IoE (Internet of Everything) thus Smart Society. To realize above-mentioned Smart Technologies, high-density, low-power consumption, wide-bandwidth, fast-operation semiconductor devices as well as smart functional devices enabled by integrating functionalities with advanced semiconductor technologies including CMOS technologies are necessary. High-density Packaging technologies such as 3D, 2.5D packaging scheme basing on TSV (through-Si via) technology and 2.1D PWB packaging are among key technologies to satisfy the requirements from the both smart semiconductor devices and smart functional devices. Meanwhile MEMS/Sensors are required as muti-functionalities of stand-alone smart devices for wearable devices including smart phone, an important part of Smart Systems. ULVAC has been continuously developing manufacturing solutions for Smart Technologies. In this talk, our high-density packaging technologies including scallop-free, low-temperature processed TSV solution for via-last packaging scheme and 2.1D packaging solutions on large panel build-up PWB will be introduced.

An integration process feasibility of backside via technology and photosensitive polymer technology using thin film battery (TFB) as a sample was investigated for realizing future 3D heterogeneous integration. Multi-layer etching by backside via process and hole-opening to photosensitive polymer for TFB insulation / wafer bonding were tried. Half-filled Cu TSV (Through Silicon Via) and polymer hole electrode formation in stacked structure for trial without thin film battery (TFB) was confirmed by cross-section SEM observation, a certain degree of feasibility for this process was shown.

We propose integrating the emergency power supply (micro Uninterruptible Power Supply, ^UPS): Integrating an energy rechargeable device on a chip to solve continuous power issue of photovoltaic cells. To realize ^UPS, we present fabrication and measurement of on-chip series-connected thin-film lithium batteries. Under the illuminated condition, series-connected PV cells directly feed multiple voltages to the system as well as charge the on-chip battery, and in case of shading it is the charged battery that feeds the system instead. The system is compatible with series-connected PV cells fabricated by CMOS MEMS post-processing. Fourteen series-connected battery was fabricated and 51.3 V was observed as the output of the battery.

Introduction Recently, all-solid-state thin-film rechargeable lithium batteries (TFBs) have expected to be used in various applications such as wireless sensor, smart device and other small devices for an auxiliary power supply. The TFBs are fabricated by forming each layers (i.e. cathode, electrolyte, anode and current collectors) mainly using physical vapor deposition process1,2). As a solid electrolyte, lithium phosphorus oxynitride (LiPON) thin film has been used commonly due to same advantages as no grain-boundary, isotropic property, less electronic conductivity and electrochemical stability. Ionic conductivity of LiPON thin film has been reported ~3.3 x 10-6 S/cm at 25 deg.C3), but it is lower compared with other solid electrolyte4). It is necessary to reduce the internal resistance of TFBs for applying to the device as described above. We tried to improve internal resistance used by Li3PO4-Li4SiO4 (LPO-LSO) electrolyte. Experimental LPO-LSO film was prepared by RF sputtering with 4 inch LPO-LSO target (Toshima manufacturing Co.). The LPO-LSO films were prepared by 0.1 Pa, 0.25 Pa and 0.6 Pa. LiPON film was prepared by RF magnetron reactive sputtering method with lithium phosphate (LPO; Li3PO4) target and N2 gas by 0.25 Pa. The substrate was glass wafer. The cathode film (LiCoO2) was prepared by RF and DC spattering method. The anode film (Metal Li) was prepared by vacuum evaporation method. Acrylic monomer was coated on the anode surface, covered with barrier lid, and cured by ultraviolet light for formation as an encapsulation. The LPO-LSO films quality were measured by FT-IR and SEM. The fabricated TFB cells were investigated by electrical and electrochemical properties at room temperature. Result and discussion Fig.1 shows the nyquist plot of Half-cell (Li/LPO-LSO/Pt, Li/LiPON/Pt) prepared by each pressure. The bulk resistance of LPO-LSO film prepared by 0.1 Pa and 0.25 Pa are lower than the bulk resistance of LiPON film. And the pressure condition of lowest bulk resistance was 0.25 Pa. Fig.2 shows the nyquist plot of TFB that electrolyte were LPO-LSO and LPO-LSO/LiPON . Two semi-circle were observed TFB that electrolyte is only LPO-LSO. We thought 1st semi-circle was the bulk resistance of LPO-LSO and 2nd semi-circle was the interfacial resistance between LPO-LSO and LiCoO2 because 2nd semi-circle was not observed in half-cell of LPO-LSO. We could improve the interfacial resistance by insertion of LiPON film (100nm) between LPO-LSO and LiCoO2. These results show LPO-LSO/LiPON electrolyte improved internal resistance of TFB. References J. B. Bates, N. J. Dudney, G. R. Gruzalski, R. A. Zuhr, A. Choudhury, C. F. Luck and J. D.Robertson, J. Power Sources, 43, 103 (1993). T. Jimbo, P. Kim and K. Suu, Energy Procedia, 14, 1574 (2012). Xiaohua Yu, J. B. Bates, G. E. Jellison, Jr., and F. X. Hart, J. Electrochem. Soc., 144, 524 (1997). N. Kamaya, K. Homma, Y. Yamakawa, M. Hirayama, R. Kanno, M. Yonemura, T. Kamiyama, Y.Kato, S. Hama, K. Kawamoto and A. Mitsui, Nature Materials, 10, 682 (2011). Figure 1

All-solid-state thin-film secondary batteries have come to be recognized as one of the key enabling technologies for stand-alone MEMS/sensor devices which are essential for internet of things. However, metallic lithium, which is commonly used as an anode layer in thin-film secondary batteries, has low melting point, so it is not applicable for high-density packaging including high-temperature process such as through-silicon via and solder-reflow process. Silicon is a promising candidate to replace metallic lithium due to high theoretical capacity. In this work, a-Si/LiPON/LiCoO2 cell which is prepared by sputtering technique confirms good reliability during 150 cycles without cracks, and also presents high-temperature tolerance.

Smart ICT (Information and Communication Technology) such as "Big Data", "Cloud computing" and Smart Functionalities such as Stand-alone Self-activating MEMS/Sensors construct Smart Systems which enable IoT (Internet of Things), IoE (Internet of Everything) thus Smart Society. To realize above-mentioned Smart Technologies, high-density, low-power consumption, wide-bandwidth, fast-operation semiconductor devices as well as smart functional devices enabled by integrating functionalities with advanced semiconductor technologies including CMOS technologies are necessary. High-density Packaging technologies such as 3D, 2.5D packaging scheme basing on TSV (through-Si via) technology and 2.1D PCB packaging are among key technologies to satisfy the requirements from the both smart semiconductor devices and smart functional devices. Meanwhile MEMS/Sensors are required as muti-functionalities of stand-alone smart devices for wearable devices including smart phone, an important part of Smart Systems. ULVAC has been continuously developing manufacturing solutions for Smart Technologies. In this talk, our high-density packaging technologies including scallop-free, low-temperature processed TSV solution for via-last packaging scheme and 2.1D packaging solutions on large panel buildup PCB will be introduced.

Telecommunication and sort-range communication will be more expansion by the internet of things. Especially, body area network (BAN) or smart-agriculture solution is able to realize the “Managed-ICT (Information and Communication Technology)” society. However, there are main three technical barriers to make this society. First is ASIC and MEMS staked sensor device fabrication. Second is a new communication protocol, which has power-saving standby, high speed and low-latency transport, and high reliability, is essential. And finally is small stand-alone battery. That is long-lifecycle, high capacity, flexible and secondary battery. The wafer/panel level packaging (WLP/PLP) technology is main solution about fusion (ASIC and MEMS-sensor) device fabrication. And, the method of wireless multi-hop network with event-driven system based on the physical layer of IEEE 802.15.4 is one of the key solutions about problem of communication protocol. This paper will describe the technology development of the process integration to make a small-die of the high-density micro thin-film lithium ion secondary stand-alone battery using by 3D packaging technologies. The thin-film battery (TFB), which structure is Ni / a-Si / LiPON / LiCoO2 / Pt / Ti / Si sub., has been developed by sputtering technology. The highly-accurate “LiPON”, “LiCoO2” and backside TSV etching technologies are necessary to miniaturization and 3D-staked. TSV etching has been developed by “Scallop-free” etching. In this research, a process for stacking functional chips using backside via technology was surveyed, mainly for platform construction of future 3D heterogeneous integration (Figure 1) to realize the “Managed - ICT” applications using by novel high-density packaging technologies.

1. Introduction Recently, all-solid-state thin-film rechargeable lithium batteries (TFBs) have expected to be used in various applications such as wireless sensor, smart device and other small devices for an auxiliary power supply. The TFBs are fabricated by forming each layers (i.e. cathode, electrolyte, anode and current collectors) mainly using physical vapor deposition process1,2). As a solid electrolyte, lithium phosphorus oxynitride (LiPON) thin film has been used commonly due to same advantages as no grain-boundary, isotropic property, less electronic conductivity and electrochemical stability. Ionic conductivity of LiPON thin film has been reported ~3.3 x 10-6 S/cm at 25 deg.C3), but it is lower compared with other solid electrolyte4). It is necessary to reduce the internal resistance of TFBs for applying to the device as described above. We improved this issue by reducing the thickness of LiPON film and reported in the previous meeting5). Internal resistance was successfully reduced. However, we had another issue that interfacial resistance between a cathode and an electrolyte was increased by planarization of a cathode surface. In this study, we investigated the mechanism of increasing of interfacial resistance and improved it with new surface modification material (LiCo0.9Al0.1O2). 2. Experimental Lithium cobalt oxide (LCO) film as a cathode was prepared by RF and DC hybrid magnetron sputtering method on platinum film as a current collector. Ar was used as sputtering gas, and process pressure was kept at 1.6 Pa. New surface modification material, LiCo0.9Al0.1O2 (LCAO) film was prepared by RF magnetron sputtering method on LCO film. Sputtering gas and process pressure were same as LCO deposition. After deposition, LCO and LCAO were annealed at 600deg.C under atmospheric pressure by lamp heating system. Solid electrolyte (LiPON) film was prepared by RF magnetron reactive sputtering method with lithium phosphate (LPO; Li3PO4) target and N2 gas. Lithium film as an anode was prepared by vacuum evaporation method. Acrylic monomer was coated on the anode surface, covered with barrier lid, and cured by ultraviolet light for formation as an encapsulation. The fabricated TFB cells were investigated by electrical and electrochemical properties at room temperature. 3. Results and discussion Figure 1 shows the scanning electron microscopy (SEM) images of LCO films with and without LCAO film after annealing process. As result , it was confirmed that top of LCO columnar grain became sharp by coating with LCAO film. We think this result shows decomposition reaction was suppressed with LCAO film. Figure 2 shows the nyquist plot of TFB and each resistance with and without LCAO film. It was also confirmed that the resistance of 1st semicircle was not changed by LCAO film thickness and the resistance of 2nd semicircle is was decreased by it. These results show LCAO film improved interfacial resistance between a cathode and an electrolyte. Reference 1) J. B. Bates, N. J. Dudney, G. R. Gruzalski, R. A. Zuhr, A. Choudhury, C. F. Luck and J. D.Robertson, J. Power Sources, 43, 103 (1993). 2) T. Jimbo, P. Kim and K. Suu, Energy Procedia, 14, 1574 (2012). 3) Xiaohua Yu, J. B. Bates, G. E. Jellison, Jr., and F. X. Hart, J. Electrochem. Soc., 144, 524 (1997). 4) N. Kamaya, K. Homma, Y. Yamakawa, M. Hirayama, R. Kanno, M. Yonemura, T. Kamiyama, Y.Kato, S. Hama, K. Kawamoto and A. Mitsui, Nature Materials, 10, 682 (2011). 5) A. Suzuki, S. Sasaki, I. Kimura and T. Jimbo, Abstract#449, 227th ECS Meeting (2015). Figure 1

Introduction Recently, smart device which enables IoT (internet of things) has induced a strong demand for high density packaging and miniaturization to fulfill high performance and functionalities simultaneously, and all-solid-state thin-film secondary batteries (TFBs) are most promising to be used as small-format and stand-alone power supplies for smart device due to intrinsically safe, high reliability and long cycle life. TFB is fabricated by forming each layers (i.e. cathode, electrolyte, anode and current collector) using physical vapor deposition process1,2), and metallic lithium is currently the most used material as an anode material in TFB. However, TFB using metallic lithium anode have thermal constraint3,4). For example, the solder-reflow process needs a thermal treatment at up to 250 deg.C, and thermal specification for automotive device is up to 150 deg.C, whereas the melting point of metallic lithium is around 180 deg.C. Therefore, other anode material in place of metallic lithium is necessary to improve high-temperature tolerance of TFB. In this work, we investigated TFB with amorphous silicon (a-Si) thin-film as an anode, and its battery performance. Experimental Lithium cobalt oxide (LCO) film was prepared by RF and DC hybrid power magnetron sputtering method on platinum film as current collector. Ar was used as sputtering gas, and process pressure was kept at 1.6 Pa. Furthermore, LCO was deposited with applying each bias power to the substrate for investigating the planarization. After deposition, LCO was annealed at 600 deg.C under atmospheric pressure by lamp heating system. Solid electrolyte (LiPON) film was prepared by RF magnetron reactive sputtering method with only N2 gas5). a-Si film as an anode was prepared by sputtering method using boron-doped silicon target. Finally, fabricated cell was encapsulated, and then “lithium-free anode” TFB was completed. Results and discussion TFB cell was fabricated with 3-μm-thick LCO, 2-μm-thick LiPON and 200-nm-thick a-Si. Figure 1 shows result of cycle performance under each SOC (state of charge), which is controlled by modulating charging cut-off voltage (3.8, 4.1, 4.2 V). Actual capacity of a-Si can be estimated from result of discharge capacity, and it was found that good cycle performance was obtained when actual capacity of a-Si anode is controlled to 2300 mAh/g. It might be considered that irreversible capacity is generated by breaking a-Si anode in a few cycles due to large volume change in results of 2750 and 3000 mAh/g. Reference; J. B. Bates, N. J. Dudney, G. R. Gruzalski, R. A. Zuhr, A. Choudhury, C. F. Luck and J. D. Robertson, J. Power Sources, 43, 103 (1993). T. Jimbo, P. Kim and K. Suu, Energy Procedia, 14, 1574 (2012). B. J. Neudecker, N. J. Dudney and J. B. Bates, J. Electrochem. Soc., 147(2), 517 (2000). V. P. Phan, B. Pecquenard and F. Le Cras, Adv. Funct. Mater., 22, 2580 (2012). A. Suzuki, S. Sasaki, I. Kimura, T. Jimbo, Abstract#449, Proceeding of 227th ECS meeting. Figure 1

"2.5D silicon interposers" and "Hetero 3D stacked" technology for high-performance LSI are gathering the most attention from now on. These technologies can solve interconnection problems using TSV (Through Silicon Via) to electrically connect stacked each function devises. 2.5D and hetero-3D Si integration has great advantages over conventional 2D devices such as high packaging density, small wire length, high-speed operation, low power consumption, and high feasibility for parallel processing. But, the radical problem about the long-term reliability of TSV production is not still solved. In particular, the management of barrier metal film deposition on the smooth surface is most important technology for Cu diffuse protection [1]. On the other hand, TSV isolation liner materials with high step coverage and lower temperature deposition on the smooth surface for high frequency devices will be necessary in the future. “Scallop-free” etching process has developed for TSV fabrication [2]. As a result, the smooth-sidewall had proved shorten PVD process time [3]. At first, it investigated a cost correlation of taper-shape etching and Cu-ECP (electrochemical plating) in this paper. And then, a polyurea film using a vapor deposition polymerization technology (which is Ulvac's FPF/PV large panel technology) tried introduction as isolation liner for next-generation high frequency device. And, it performed the film formation to a TSV pattern.

In recent years, "2.5D silicon interposers" and "Full 3D stacked" technology for high-performance LSI has attracted much attention since this technology can solve interconnection problems using TSV (Through Silicon Via) to electrically connect stacked LSI. 2.5D and 3D Si integration has great advantages over conventional 2D devices such as high packaging density, small wire length, high-speed operation, low power consumption, and high feasibility for parallel processing. But, the radical problem about the TSV production cost is not still solved. In particular, the demand to a new plating bath technology to shorten Cu plating time is expected. On the other hand, TSV isolation liner materials with lower cost for high frequency devices will be necessary in future. “Scallop-free” etching process has developed for TSV fabrication [1]. And, the smooth-sidewall had proved shorten PVD process time [2]. At first, it investigated a cost correlation of taper-shape etching and Cu-ECP (electrochemical plating) in this paper. And then, a polyurea film using a vapor deposition polymerization technology (which is Ulvac's FPF/PV large panel technology) tried introduction as isolation liner for next-generation high frequency device. And, it performed the film formation to a TSV pattern.