智能剥离工艺的热动力学模型(英文)

提出了注氢硅片表面借助键合氧化硅片进行剥离的热动力学模型 ,这种剥离现象是退火过程中氢离子注入区氢气泡横向增长的结果 .氢气泡的增长速率依赖于氢复合体分解和氢分子扩散所需的激活能 ,氢气泡的半径是退火时间、退火温度和注氢剂量的函数 .氢气泡的临界半径可根据 Griffith能量平衡条件来获得 .根据氢气泡增长的这一临界条件 ,获得了不同劈裂温度时所需的剥离时间     

Silicon layer transfer using wafer bonding and debonding

Two experiments were performed that demonstrate an extension of the ion-cut layer transfer technique where a polymer is used for planarization and bonding. In the first experiment hydrogen-implanted silicon wafers were deposited with two to four microns low-temperature plasma-enhanced tetraethoxysilane (TEOS). The wafers were then bonded to a second wafer, which had been coated with a spin-on polymer. The bonded pairs were heated to the ion-cut temperature resulting in the transfer of a 400 nm layer silicon. The polymer enabled the bonding of an unprocessed silicon wafer to the as-deposited TEOS with a microsurface roughness larger than 10 nm, while the TEOS provided sufficient stiffness for ion cut. In the second experiment, an intermediate transfer wafer was patterned and vias were etched through the wafer using a 25% tetramethylammonium hydroxide (TMAH) solution and nitride as masking material. The nitride was then stripped using dilute hydrofluoric acid (HF). The transfer wafer was then bonded to an oxidized (100 nm) hydrogen-implanted silicon wafer. After ion-cut annealing a silicon-on-insulator (SOI) wafer was produced on the transfer wafer. The thin silicon layer of the SOI structure was then bonded to a third wafer using a spin-on polymer as the bonding material. The sacrificial oxide layer was then etched away in HF, freeing the thin silicon from the transfer wafer. The result produced a thin silicon-on-polymer structure bonded to the third wafer. These results demonstrate the feasibility of transferring a silicon layer from a wafer to a second intermediate “transfer” or “universal” reusable substrate. The second transfer step allows the thin silicon layer to be subsequently bonded to a potential third device wafer followed by debonding of the transfer wafer creating stacked three-dimensional structures.     

Diffusion‐free high efficiency silicon solar cells

Traditional POCl₃ diffusion is performed in large diffusion furnaces heated to ~850 C and takes an hour long. This may be replaced by an implant and subsequent 90‐s rapid thermal annealing step (in a firing furnace) for the fabrication of p‐type passivated emitter rear contacted silicon solar cells. Implantation has long been deemed a technology too expensive for fabrication of silicon solar cells, but if coupled with innovative process flows as that which is mentioned in this paper, implantation has a fighting chance. An SiOx/SiN_y rear side passivated p‐type wafer is implanted at the front with phosphorus. The implantation creates an inactive amorphous layer and a region of silicon full of interstitials and vacancies. The front side is then passivated using a plasma‐enhanced chemical vapor deposited SiN_xH_y. The wafer is placed in a firing furnace to achieve dopant activation. The hydrogen‐rich silicon nitride releases hydrogen that is diffused into the Si, the defect rich amorphous front side is immediately passivated by the readily available hydrogen; all the while, the amorphous silicon recrystallizes and dopants become electrically active. It is shown in this paper that the combination of this particular process flow leads to an efficient Si solar cell. Cell results on 160‐µm thick, 148.25‐cm² Cz Si wafers with the use of the proposed traditional diffusion‐free process flow are up to 18.8% with a V_oc of 638 mV, J_sc of 38.5 mA/cm², and a fill factor of 76.6%. Copyright © 2012 John Wiley & Sons, Ltd.     

X-ray-emission study of the structure of Si:H layers formed by low-energy hydrogen-ion implantation

Amorphous silicon layers formed by implantation of 24-keV hydrogen ions into SiO₂/Si and Si with doses of 2.7×10¹⁷ and 2.1×10¹⁷ cm^?2, respectively, were studied using ultrasoft X-ray emission spectroscopy with variations in the energy of excitation electrons. It is ascertained that the surface silicon layer with a thickness as large as 150–200 nm is amorphized as a result of implantation. Implantation of hydrogen ions into silicon coated with an oxide layer brings about the formation of a hydrogenated silicon layer, which is highly stable thermally.     

Electrical conductivity of silicon-on-insulator structures prepared by bonding silicon wafers to a substrate using hydrogen implantation

Silicon-on-insulator structures were prepared by exfoliating a thin layer from a silicon wafer owing to hydrogen implantation, transferring this layer to another substrate, and bonding to it. The influence of hydrogen and the doping level in the original wafers on the free-carrier concentration and the conductivity type in the split-off silicon layer was investigated. A high boron concentration in the original material, together with a high concentration of residual hydrogen in the silicon layer exfoliated from the wafer, was shown to result in n-type conduction, which is retained up to annealing temperatures of 1100°C in these structures. A decrease in the residual hydrogen concentration owing to additional annealing creates the conditions under which the conductivity of resulting structures corresponds to the conductivity type of the original material.     

Current transport in fluorine implanted GaAs

Effects of fluorine implantation in GaAs have been investigated by electrical characterization. Ion implantation at 100 keV energy was conducted with doses of 10¹¹ and 10¹²/cm². The effect of fluorine implantation on current-voltage (I-V) characteristics of Schottky diodes was significant. Carrier compensation was observed after implantation by the improved I-V characteristics. The lower dose implanted samples showed thermionic emission dominated characteristics in the measurement temperature range of 300 to 100K. The starting wafer and the low dose implanted samples after rapid thermal annealing (RTA) showed similar I-V properties with excess current in the lower temperature range dominated by recombination. The higher dose implanted samples showed increased excess current in the whole temperature range which may result from the severe damage-induced surface recombination. These samples after RTA treatment did not recover from implantation damage as in the low dose implantation case. However, very good I-V characteristics were seen in the higher dose implanted samples after RTA. The influence of the higher dose ion implantation was to produce more thermal stability. The results show the potential application of fluorine implantation in GaAs device fabrication.     

Transfer of semiconductor and oxide films by wafer bonding and layer cutting

Material integration by wafer bonding and layer transfer is one of the main approaches to increase functionality of semiconductor devices and to enhance integrated circuits (IC) performance. Even though most mismatches such as different lattice constants betweeen bonding materials present no obstacle for wafer direct bonding, thermal stresses caused by thermal mismatches must be minimized by low temperature bonding to avoid debonding, sliding or cracking. In order to achieve a strong bond at low temperatures, two approaches may be adopted: 1) Bonding at room temperature by hydrogen bonding of OH, NH, or FH terminated surfaces followed by polymerization to form covalent bonds. Within this approach the key is to remove the by-products of the reaction at the bonding interface. 2) Direct formation of a covalent bond between clean surfaces without adsorbents in ultra high vacuum conditions. Low temperature bonding allows bonding processed wafers for technology integration. Layer transfer requires uniform thinning of one wafer of a bonded pair. The most promising technology involves a buried embrittled region by hydrogen implantation. A layer with a thickness corresponding to the hydrogen implantation depth is then transferred onto a bonded desired substrate by either splitting due to internal gas pressure or by forced peeling as long as the bonding energy is higher than the fracture energy in the embrittled region at the layer transfer temperature. This approach is quite generic in nature and may be applied to almost all materials. We have found that B+H co-implantation and/or H implantation at high temperatures can significantly lower the splitting temperature. However, the wafer temperature during H implantation has to be within a temperature window that is specific for each material. The experimentally determined temperature windows for some semiconductors and single crystalline oxides will be given.     

Pressure-induced formation of thermal donor centers in silicon after oxygen ion bombardment

This paper discusses the generation of thermal donor centers in silicon by oxygen ion implantation in the temperature range 350 to 550 °C. These donors are distributed almost uniformly over the entire thickness of the silicon crystals and well outside the region of direct penetration of the ions. It is established that implantation of Czochralski-grown silicon with oxygen ions followed by annealing accelerates the introduction of these donors into the silicon, and that application of hydrostatic pressure further accelerates the process of donor-center formation. The data indicate that this accelerated introduction of donors is associated with diffusion of radiation-induced defects from the implanted layer into the crystal bulk, and that the diffusion coefficients of these defects are 1×10⁻⁷ cm²/s or larger. Fiz. Tekh. Poluprovodn. 33, 1153–1157 (October 1999)     

Plasma immersion ion implantation for SOI synthesis: SIMOX and ion-cut

We have demonstrated feasibility to form silicon-on-insulator (SOI) substrates using plasma immersion ion implantation (PIII) for both separation by implantation of oxygen and ion-cut. This high throughput technique can substantially lower the high cost of SOI substrates due to the simpler implanter design as well as ease of maintenance. For separation by plasma implantation of oxygen wafers, secondary ion mass spectrometry analysis and cross-sectional transmission electron micrographs show continuous buried oxide formation under a single-crystal silicon overlayer with sharp Si/SiO₂ interfaces after oxygen plasma implantation and high-temperature (1300°C) annealing. Ion-cut SOI wafer fabrication technique is implemented for the first time using PIII. The hydrogen plasma can be optimized so that only one ion species is dominant in concentration and there are minimal effects by other residual ions on the ion-cut process. The physical mechanism of hydrogen induced silicon surface layer cleavage has been investigated. An ideal gas law model of the microcavity internal pressure combined with a two-dimensional finite element fracture mechanics model is used to approximate the fracture driving force which is sufficient to overcome the silicon fracture resistance.     

Solar‐grade boron emitters by BF3 plasma doping and role of the co‐implanted fluorine

We investigate the electrical properties and dopant profiles of boron emitters performed by plasma immersion ion implantation from boron trifluoride (BF₃) gas precursor, thermally annealed and passivated by silicon oxide/silicon nitride stacks. High thermal budgets are required for doses compatible with screen‐printed metal pastes, to reach very good activation rates. However, if good sheet resistances and saturation current densities may be obtained, we met strong limitations of the implied open‐circuit voltage of the n‐type Czochralski silicon substrates, which is incompatible with high‐efficiency solar cells. Such limitations are not encountered with beamline where pure B⁺ ions are implanted. Efforts on the passivation quality may improve the implied open‐circuit voltage but are not sufficient. We provide experimental comparison between beamline and plasma immersion allowing us to discriminate the causes explaining this observation (implantation technique or ion specie used) and to infer our interpretation: The co‐implantation of fluorine seems to indirectly impact the lifetime of the core substrate after thermal annealing. Copyright © 2015 John Wiley & Sons, Ltd.     

用于制备SOI材料的基于硅片键合和双层多孔硅剥离的薄外延硅膜转移技术

采用在阳极化反应时改变电流强度的办法 ,在高掺杂的 P型硅 (111)衬底上制备了具有不同多孔度的双层结构多孔硅层 .用超高真空电子束蒸发技术在多孔硅表面外延生长了一层高质量的单晶硅膜 .在室温下 ,该外延硅片同另一生长有热二氧化硅的硅片键合在一起 ,在随后的热处理过程中 ,键合对可在多孔硅处裂开 ,从而使外延的单晶硅膜转移到具有二氧化硅的衬底上以形成 SOI结构 .扫描电镜、剖面投射电镜、扩展电阻和霍尔测试表明 SOI样品具有较好的结构和电学性能     

High-quality crystalline layer transfer from a silicon-on-insulator substrate onto a sapphire substrate using wafer bonding

We demonstrate layer transfer of 150 nm of Si from a 200-mm, silicon-on-insulator (SOI) substrate onto a sapphire substrate using low-temperature wafer bonding (T=150°C). The crystalline quality and the thermal stability of the transferred Si layer were characterized by x-ray diffraction (XRD). A broadening of the (004) Si peak is observed only for anneal temperatures T_A≥800°C, indicating some degradation of the crystalline quality of the transferred Si film above these temperatures. The measured electron Hall mobility in the bonded Si layer is comparable to bulk silicon for T_A≤800°C, indicating excellent material quality.     

用于制备SOI材料的基于硅片键合和双层多孔硅剥离的薄外延硅膜转移技术

采用在阳极化反应时改变电流强度的办法,在高掺杂的P型硅(111)衬底上制备了具有不同多孔度的双层结构多孔硅层.用超高真空电子束蒸发技术在多孔硅表面外延生长了一层高质量的单晶硅膜.在室温下,该外延硅片同另一生长有热二氧化硅的硅片键合在一起,在随后的热处理过程中,键合对可在多孔硅处裂开,从而使外延的单晶硅膜转移到具有二氧化硅的衬底上以形成SOI结构.扫描电镜、剖面投射电镜、扩展电阻和霍尔测试表明SOI样品具有较好的结构和电学性能.     

Study of silicon doped with zinc ions and annealed in oxygen

The results of studies of the surface layer of silicon and the formation of precipitates in Czochralski n-Si (100) samples implanted with ⁶⁴Zn⁺ ions with an energy of 50 keV and a dose of 5 × 10¹⁶ cm^–2 at room temperature and then oxidized at temperatures from 400 to 900°C are reported. The surface is visualized using an electron microscope, while visualization of the surface layer is conducted via profiling in depth by elemental mapping using Auger electron spectroscopy. The distribution of impurity ions in silicon is analyzed using a time-of-flight secondary-ion mass spectrometer. Using X-ray photoelectron spectroscopy, the chemical state of atoms of the silicon matrix and zinc and oxygen impurity atoms is studied, and the phase composition of the implanted and annealed samples is refined. After the implantation of zinc, two maxima of the zinc concentration, one at the wafer surface and the other at a depth of 70 nm, are observed. In this case, nanoparticles of the Zn metal phase and ZnO phase, about 10 nm in dimensions, are formed at the surface and in the surface layer. After annealing in oxygen, the ZnO · Zn₂SiO₄ and Zn · ZnO phases are detected near the surface and at a depth of 50 nm, respectively.     

Fabrication and Characterization of 150-mm Silicon-on-Polycrystalline Silicon Carbide Substrates

Silicon-on-insulator (SOI) substrates can reduce radiofrequency (RF) substrate losses due to their buried oxide (BOX). On the other hand, the BOX causes problems since it acts as a thermal barrier. Oxide has low thermal conductivity and traps heat generated by devices on the SOI. This paper presents a hybrid substrate which uses a thin layer of polycrystalline silicon and polycrystalline silicon carbide (Si-on-poly-SiC) to replace the thermally unfavorable BOX and the silicon substrate. Substrates of 150 mm were fabricated by wafer bonding and shown to be stress and strain free. Various electronic devices and test structures were processed on the hybrid substrate as well as on a low-resistivity SOI reference wafer. The substrates were characterized electrically and thermally and compared with each other. Results showed that the Si-on-poly-SiC wafer had 2.5 times lower thermal resistance and exhibited equal or better electrical performance compared with the SOI reference wafer.     

Exfoliation and blistering of Cd<Subscript>0.96</Subscript>Zn<Subscript>0.04</Subscript>Te substrates by ion implantation

As part of a series of wafer bonding experiments, the exfoliation/blistering of ion-implanted Cd_0.96Zn_0.04Te substrates was investigated as a function of postimplantation annealing conditions. (211) Cd_0.96Zn_0.04Te samples were implanted either with hydrogen (5×10¹⁶ cm⁻²; 40–200 keV) or co-implanted with boron (1×10¹⁵ cm⁻²; 147 keV) and hydrogen (1–5×10¹⁶ cm⁻²; 40 keV) at intended implant temperatures of 253 K or 77 K. Silicon reference samples were simultaneously co-implanted. The change in the implant profile after annealing at low temperatures (<300°C) was monitored using high-resolution x-ray diffraction, atomic force microscopy (AFM), and optical microscopy. The samples implanted at the higher temperature did not show any evidence of blistering after annealing, although there was evidence of sample heating above 253 K during the implant. The samples implanted at 77 K blistered at temperatures ranging from 150°C to 300°C, depending on the hydrogen implant dose and the presence of the boron co-implant. The production of blisters under different implant and annealing conditions is consistent with nucleation of subsurface defects at lower temperature, followed by blistering/exfoliation at higher temperature. The surface roughness remained comparable to that of the as-implanted sample after the lower temperature anneal sequence, so this defect nucleation step is consistent with a wafer bond annealing step prior to exfoliation. Higher temperature anneals lead to exfoliation of all samples implanted at 77 K, although the blistering temperature (150–300°C) was a strong function of the implant conditions. The exfoliated layer thickness was 330 nm, in good agreement with the projected range. The “optimum” conditions based on our experimental data showed that implanting CdZnTe with H⁺ at 77 K and a dose of 5×10¹⁶/cm² is compatible with developing high interfacial energy at the bonded interface during a low-temperature (150°C) anneal followed by layer exfoliation at higher (300°C) temperature.     

Bonding and thermal stability of implanted hydrogen in silicon

The behavior of implanted hydrogen in Si has been investigated by differential infrared transmittance measurements using multiple-internal-reflection (MIR) plates. Si-H bonding of implanted hydrogen is detected by seven absorption bands between 4.5 and 5.5 μm after implantation with 10¹⁶ H⁺/cm² at ion energies between 70 and 400 keV. The absorption bands are close in frequency to those for SiH stretching modes for silane, and they are produced only by hydrogen implantation. Implantation with deuterium gave absorption bands shifted to lower frequencies in accord with the square root of the reduced mass ratio for Si-H relative to Si-D. The multiplicity of hydrogen-associated bands is apparently a consequence of defects in the implanted layer. A dependence of the hydrogen-associated bands on the disorder is suggested by the annealing loss of five of the initial seven bands, and a growth of the other two, for the same temperatures (100–300°C) as those for annealing out the broad divacancy band at 1.8 μm. A disorder dependence of the Si-H vibrational frequencies is further demonstrated by a regeneration of the bands annealing below 300°C when a hydrogen-implanted MIR plate annealed at 300°C was subsequently bombarded with neon. In addition to the seven resolved bands after H⁺ implantation, five other bands in the same range of frequencies grow in and anneal out between 100 and 700°C. Annealing at 700°C eliminates all SiH bands, and they cannot be regenerated by bombardment with other ions. It is suggested that implanted hydrogen in Si is bonded at defect sites, and that a loss of an SiH band is caused by either a change in charge state of a defect or by the loss of a defect. This work was supported by the United States Atomic Energy Commission     

硅/玻璃紫外固化中间层键合

利用玻璃的透光特性和紫外固化的成熟技术,研究了一种使用紫外固化胶作为中间层的玻璃/硅室温键合工艺.通过选择一定波段的紫外固化胶,旋涂紫外胶后使用365nm光刻机作为紫外光源控制紫外固化,从而实现了硅/玻璃的中间层键合.分析测试结果表明,紫外固化辅助的中间层键合可以成功应用于硅/玻璃键合,中间层厚5～6μm,键合强度达到26MPa.该工艺只需室温条件,简单高效,成本低廉,无需额外的压力或电场,对于硅/玻璃低温键合封装具有潜在的应用价值.     

Titanium Disilicide as High-Temperature Contact Material for Thermoelectric Generators

Thermoelectric devices can be used to capture electric power from waste heat in a variety of applications. The theoretical efficiency rises with the temperature difference across the thermoelectric generator (TEG). Therefore, we have investigated contact materials to maximize the thermal stability of a TEG. A promising candidate is titanium disilicide (TiSi₂), which has been well known as a contact material in silicon technology for some time, having low resistivity and thermal stability up to 1150 K. A demonstrator using highly doped silicon as the thermoelectric material has been integrated. A p- and an n-type wafer were oxidized and bonded. After cutting the wafer into pieces, a 200-nm-thick titanium layer was sputtered onto the edges. After a 750°C rapid thermal annealing step, the TEG legs were connected by a highly conductive TiSi₂ layer. A TEG with 12 thermal couples was integrated, and its joint resistance was found to be 4.2 Ω. Hence, we have successfully demonstrated a functional high-temperature contact for TEGs up to at least 900 K. Nevertheless, the actual thermal stability will be even higher. The process could be transfered to other substrates by using amorphous silicon deposited by plasma-enhanced chemical vapor deposition.     

Germanium on sapphire by wafer bonding

This paper describes the creation of a germanium on sapphire platform, via wafer bonding technology, for system-on-a-chip applications. Similar thermal coefficients of expansion between germanium (5.8 × 10^?6 K^?1) and sapphire (5 × 10^?6 K^?1) make the bonding of germanium to sapphire a reality. Germanium directly bonded to sapphire results in microvoid generation during post bond annealing. Inclusion of an interface layer such as silicon dioxide layer by plasma enhanced chemical vapour deposition, prior to bonding, results in a microvoid free bond interface after annealing. Grinding and polishing of the subsequent germanium layer has been achieved leaving a thick germanium on sapphire (GeOS) substrate. Submicron GeOS layers have also been achieved with hydrogen/helium co-implantation and layer transfer. Circular geometry transistors exhibiting a field effect mobility of 890 cm²/V s have been fabricated onto the thick germanium on sapphire layer.