单晶硅中过渡族金属镍对洁净区形成的影响

研究了过渡族金属镍在快速热处理作用下对直拉单晶硅中洁净区形成的影响.实验结果发现:硅中魔幻洁净区(MDZ)形成后,氧沉淀及其诱生缺陷能有效地吸杂金属镍;而沾污金属镍的硅中,随后的快速热处理工艺不能形成MDZ,硅片近表面出现大量沉淀.采用传统的内吸杂工艺,镍沾污的次序对洁净区的形成没有影响.实验表明由于硅片表面形成的镍硅化合物的晶格常数比硅小,所以在硅片近表面产生高浓度的空位,导致近表面的氧依然能够在MDZ工艺中形成沉淀.     

铜镍共沉淀对直拉硅单晶中洁净区形成的影响

The influence of co-precipitation of copper and nickel on the formation of a denuded zone(DZ) in Czochralski silicon(Cz Si) was systematically investigated by means of etching and optical microscopy(OM).It was found that,for conventional high-low-high annealing(CFA),the DZ could be obtained in all specimens contaminated by copper and nickel co-impurity at different steps of the heat treatment,indicating that no copper precipitates or nickel precipitates were generated in the region just below the surface.However,for rapid thermal annealing(RTA)-low-high annealing,the tendency is not the same; the DZ could not be found in the specimen which was contaminated by copper and nickel contamination before the first RTA annealing.On the basis of the experimental results,it was supposed that the concentration and distribution of the vacancies generating during the RTA can influence the distribution of copper precipitation and nickel precipitation along the cross-section of Cz Si significantly,and thus influence the formation of the DZ to a great extent.     

NiSi/Si界面的剖面透射电镜研究

采用不同硅化工艺制备了NiSi薄膜并用剖面透射电镜(XTEM)对样品的NiSi/Si界面进行了研究.在未掺杂和掺杂(包括As和B)的硅衬底上通过物理溅射淀积Ni薄膜,经快速热处理过程(RTP)完成硅化反应.X射线衍射和喇曼散射谱分析表明在各种样品中都形成了NiSi.还研究了硅衬底掺杂和退火过程对NiSi/Si界面的影响.研究表明:使用一步RTP形成NiSi的硅化工艺,在未掺杂和掺As的硅衬底上,NiSi/Si界面较粗糙;而使用两步RTP形成NiSi所对应的NiSi/Si界面要比一步RTP的平坦得多.高分辨率XTEM分析表明,在所有样品中都形成了沿衬底硅〈111〉方向的轴延-NiSi薄膜中的一些特定晶面与衬底硅中的(111)面对准生长.同时讨论了轴延中的晶面失配问题.     

大直径直拉硅片的快速热处理

主要研究了快速热处理( RTP)对大直径直拉( CZ)硅片的清洁区( DZ)和氧沉淀的影响.通过在Ar、N2 、O2 三种不同气氛中,在不同温度下RTP发现在大直径CZ硅片中氧沉淀的行为及DZ的宽度与RTP的温度、气氛有很大关系.在实验的基础上,讨论了在大直径CZ硅中RTP对氧沉淀和DZ的影响机理.     

Study of NiSi/Si Interface by Cross-Section Transmission Electron Microscopy

采用不同硅化工艺制备了NiSi薄膜并用剖面透射电镜(XTEM)对样品的NiSi/Si界面进行了研究.在未掺杂和掺杂(包括As和B)的硅衬底上通过物理溅射淀积Ni薄膜,经快速热处理过程(RTP)完成硅化反应.X射线衍射和喇曼散射谱分析表明在各种样品中都形成了NiSi.还研究了硅衬底掺杂和退火过程对NiSi/Si界面的影响.研究表明:使用一步RTP形成NiSi的硅化工艺,在未掺杂和掺As的硅衬底上,NiSi/Si界面较粗糙;而使用两步RTP形成NiSi所对应的NiSi/Si界面要比一步RTP的平坦得多.高分辨率XTEM分析表明,在所有样品中都形成了沿衬底硅〈111〉方向的轴延-NiSi薄膜中的一些特定晶面与衬底硅中的(111)面对准生长.同时讨论了轴延中的晶面失配问题.     

Influence of the Surface Layer on the Electrochemical Deposition of Metals and Semiconductors into Mesoporous Silicon

The influence of the surface layer on the process of the electrochemical deposition of metals and semiconductors into porous silicon is studied. It is shown that the surface layer differs in structure and electrical characteristics from the host porous silicon bulk. It is established that a decrease in the conductivity of silicon crystallites that form the surface layer of porous silicon has a positive effect on the process of the filling of porous silicon with metals and semiconductors. This is demonstrated by the example of nickel and zinc oxide. The effect can be used for the formation of nanocomposite materials on the basis of porous silicon and nanostructures with a high aspect ratio.     

直拉单晶硅中氧沉淀的高温消融和再生长

重点研究了直拉(CZ)硅中氧沉淀在快速热处理(RTP)和常规炉退火过程中的高温消融以及再生长行为.实验发现,RTP是一种快速消融氧沉淀的有效方式,比常规炉退火消融氧沉淀更加显著.硅片经RTP消融处理后,在氧沉淀再生长退火过程中,硅中体微缺陷(BMD)的密度显著增加,BMD的平均尺寸略有增加;而经过常规炉退火消融处理后,在后续退火过程中,BMD的密度变化不大,但BMD的尺寸明显增大.氧沉淀消融处理后,后续退火的温度越高,氧沉淀的再生长越快.     

Understanding and implementation of rapid thermal technologies forhigh-efficiency silicon solar cells

Rapid and potentially low-cost process techniques are analyzed and successfully applied toward the fabrication of high-efficiency monocrystalline Si solar cells. First, a methodology for achieving high-quality screen-printed (SP) contacts is developed to achieve fill factors (FF's) of 0.785-0.795 on monocrystalline Si. Second, rapid emitter formation is accomplished by diffusion under tungsten halogen lamps in both beltline and rapid thermal processing (RTP) systems (instead of in a conventional infrared furnace). Third, a combination of SP aluminum and RTP is used to form an excellent back surface field (BSF) in 2 min to achieve an effective back surface recombination velocity (S_eff) of 200 cm/s on 2.3 Ω-cm Si. Next, a novel dielectric passivation scheme (formed by stacking a plasma silicon nitride film on top of a rapid thermal oxide layer) is developed that reduces the surface recombination velocity (S) to approximately 10 cm/s on the 1.3 Ω-cm p-Si surface. The essential feature of the stack passivation scheme is its ability to withstand short 700-850°C anneal treatments (like the ones used to fire SP contacts) without degradation in S. The stack also lowers the emitter saturation current density (J_oe) of 40 and 90 Ω/sq emitters by a factor of three and ten, respectively, compared to no passivation. Finally, the above individual processes are integrated to achieve (1) >19% efficient solar cells with emitter and Al-BSF formed by RTP and contacts formed by vacuum evaporation and lift-off, (2) 17% efficient manufacturable cells with emitter and Al-BSF formed in a beltline furnace and contacts formed by SP, and (3) 17% efficient gridded-back contact (bifacial) cells with surface passivation accomplished by the stack and gridded front and back contacts formed by SP and cofiring     

Manufacturability issues related to transient thermal annealing oftitanium silicide films in a rapid thermal processor

Transient thermal annealing of sputtered titanium films in a rapid thermal processor (RTP) is critically evaluated from the viewpoint of manufacturability-related considerations. In particular, the thin-film properties of the resulting titanium silicide on polysilicon and silicon, process uniformity, and unit step wafer yield of high-density scaled device structures are investigated. The experimental results suggest that RTP silicides show good thin-film properties for manufacturability on planar wafer surfaces. Transient thermal gradients in an RTP system are shown to cause substantial variations in the electrical and structural properties of TiSi_x films formed on silicon substrates with varying substrate thicknesses. Closed-loop temperature control in an RTP reactor provided stoichiometrically identical TiSi_x films with negligible substrate thickness dependence. The experimental results also suggest that careful wafer surface temperature control is needed when forming titanium silicide films on nonplanar silicon surfaces, silicon trenches, and process monitor wafers without predetermined wafer thicknesses     

Low temperature RTP for BCB curing

Rapid thermal processing (RTP) applications are rapidly expanding from the original processes, typically performed above 1000 °C (e.g., post-implant annealing and silicon oxidation) to lower temperature applications such as cobalt and nickel silicide formation with process steps performed as low as 200 °C. The original lamp-based (i.e., “cold wall”) RTP systems, despite their pyrometry-related issues, are [1] still used, even in this low temperature regime. Another problem related to this approach occurs when processing materials exhibit significant outgassing, such as boron-phosphosilicate glass (BPSG). The outgassed vapour can condense on the cold chamber walls and change the light transmission characteristics of the quartz window. This can cause a process shift, uniformity change and will likely increase maintenance. In this paper, an alternative, hot wall approach, based on convection and conductive heat transfer is evaluated for low-temperature curing and annealing of benzocyclobutene (BCB) for high speed digital and microwave applications [2].     

Rapid thermal processing of next generation silicon solar cells

Rapid and potentially low‐cost process techniques are analyzed and successfully applied towards the fabrication of high‐efficiency mono‐ and multicrystalline Si solar cells. First, a novel dielectric passivation scheme (formed by stacking a plasma silicon nitride film on top of a rapid thermal oxide layer) is developed that serves as antireflection coating and reduces the surface recombination velocity (S_eff) of the 1˙3 Ω‐cm p‐Si surface to approximately 10 cm/s. The essential feature of the stack passivation scheme is its ability to withstand short 700 – 850°C anneal treatments used to fire screen printed (SP) contacts, without degradation in S_oeff. The stack also lowers the emitter saturation current density (J_oe) of 40 and 90 Ω/□ emitters by a factor of three and 10, respectively, compared to no passivation. Next, rapid emitter formation is accomplished by diffusion under tungsten halogen lamps in both belt line and rapid thermal processing (RTP) systems (instead of in a conventional infrared furnace) . Third, a combination of SP aluminium and RTP is used to form an excellent back surface field (BSF) in 2 min to achieve an effective back surface recombination velocity (S_eff) of 200 cm/s on 2˙3 Ω‐cm Si. Finally, the above individual processes are integrated to achieve: (1) >19% efficient solar cells with emitter and Al‐BSF formed by RTP and contacts formed by vacuum evaporation and photolithography, (2) 17% efficient manufacturable cells with emitter and Al‐BSF formed in a belt line furnace and contacts formed by SP. Copyright © 2000 John Wiley & Sons, Ltd.     

Impact of surface preparation on nickel-platinum alloy silicide phase formation

Nickel based silicide films were prepared by annealing nickel-platinum layers deposited on n-doped Si substrates. We report on the evolution of the crystallography, the phase formation and the redistribution of contaminants on blanket wafers during silicide formation as a function of the silicon surface preparation prior to Ni(Pt) deposition. In situ argon sputtering etch creates a contamination layer which modifies phase texture during the formation of the first Ni silicide phases. Using remote pre-clean results in a predominant Ni₂Si phase with preferential grain orientation after a first anneal. After a second anneal, the monosilicide forms, regardless of what nickel rich silicide phase was initially formed and regardless of the surface preparation prior to metal deposition.     

Impact of Transition-Metal Contamination on Oxygen Precipitation in Czochralski Silicon Under Rapid Thermal Processing

研究了快速热处理工艺下直拉单晶硅中过渡族金属铜、镍对内吸杂工艺中氧沉淀形成规律的影响.实验结果表明:在快速热处理工艺下,间隙铜对氧沉淀几乎没有影响,铜沉淀却能显著地促进氧沉淀的形成;而间隙镍或镍沉淀对氧沉淀的形成都没有影响.基于实验结果并结合氧沉淀的形核理论,对金属铜、镍对氧沉淀的影响机理进行了解释.     

快速热处理工艺下直拉单晶硅中铜、镍对氧沉淀的影响

研究了快速热处理工艺下直拉单晶硅中过渡族金属铜、镍对内吸杂工艺中氧沉淀形成规律的影响.实验结果表明:在快速热处理工艺下,间隙铜对氧沉淀几乎没有影响,铜沉淀却能显著地促进氧沉淀的形成;而间隙镍或镍沉淀对氧沉淀的形成都没有影响.基于实验结果并结合氧沉淀的形核理论,对金属铜、镍对氧沉淀的影响机理进行了解释.     

Electroless nickel/gold bump in the flip-chip-type CMOS package for mobile-phone camera modules

Wafer bumping technology using electroless nickel bump with a thin gold layer was studied for the flip-chip-type CMOS image-sensor (CIS) package for mobile-phone camera modules. The precise control of process parameters in the electroless nickel solution was undertaken by synthetic consideration of the effects of solution temperature, pH, stabilizer concentration, and aluminum pad size on the electroless nickel/gold bump formation. The flip-chip bonding process fitting the electroless nickel/gold bump is conducted by optimization of bonding temperature, pressure, and time. Reliability tests are performed to ensure the robustness of the image-sensor module. The impurity particle density is estimated to be one per 300,000 pixels by 3D laser analysis on the image-sensor surface. The phenomenon of the drop in chip yield during the wet process is attributed to the organic particles produced during the wafer backside coating. From all the experimental results, we first suggest that electroless nickel/gold can be applied to flip-chip-type CIS package for the mobilephone camera module without any significant impurity contamination of the image-sensor surface.     

Study of nickel contamination on the ultrasonic bondability of gold bond finger of SD-48L packages

Contamination is a major barrier to the adhesion of solid-phase metal couples. If me-tallic impurities are present on a gold (Au) bonding surface, it can easily react with oxygen molecules in the atmosphere to form oxides. The oxides formed prevent intimate metal-metal contact which is important for bond formation. A study is carried out to investigate whether nickel (Ni) contamination can affect the ultrasonic bondability of Au bond finger of side-braze 48-lead ceramic package. Two sets of samples are used for this study. The first set comprising uncontaminated packages serves as a control group. The second set are Ni contaminated packages. The results of the study show that Ni contamination does not affect the ultrasonic bondability of the Au bond finger. A second study to ascertain the quality of the wire bonds however shows that the mean bond tensile strength of the Ni contaminated packages has weakened slightly.     

18% efficient silicon photovoltaic devices by rapid thermaldiffusion and oxidation

For the first time, cells formed by rapid thermal processing (RTP) have resulted in 18%-efficient 1 and 4 cm² single-crystal silicon solar cells. Front surface passivation by rapid thermal oxidation (RTO) significantly enhanced the short wavelength response and decreased the effective front surface recombination velocity (including contact effects) from 7.5×10⁵ to about 2×10⁴ ×10⁴ cm/s. This improvement resulted in an increase of about 1% (absolute) in energy conversion efficiency, up to 20 mV in V_ot, and about 1 mA/cm² in J_sc. These RTO-induced enhancements are shown to be consistent with model calculations. Since only 3 to 4 min are required to simultaneously form the phosphorus emitter and aluminum back-surface-field (BSF) and 5 to 6 min are required for growing the RTO, this RTP/RTO process represents the fastest technology for diffusing and oxidizing ⩾18%-efficient solar cells. Both cycles incorporate an in situ anneal lasting about 1.5 min to preserve the minority carrier lifetime of lower quality materials such as dendritic-web and multicrystalline silicon. These high-efficiency cells confirmed that RTP results in equivalent performance to cells fabricated by conventional furnace processing (CFP). Detailed characterization and modeling reveals that because of RTO passivation of the front surface (which reduced J_0c by nearly a factor of ten), these RTP/RTO cells have become base dominated (J_0b≫J_0c), and further improvement in cell efficiency is possible by a reduction in back surface recombination velocity (BSRV). Based upon model calculations, decreasing the BSRV to 200 cm/s is expected to give 20%-efficient RTP/RTO cells     

The silicon-silicon dioxide system

Study of the silicon-silicon dioxide system as a junction between a nearly ideal semiconductor and insulator has aroused both scientific and technological interest. Surface phenomena associated with this system are influenced by contamination and imperfections in the oxide, impurity redistribution in the silicon near the oxide, and finally by additional electronic energy states at the oxide-silicon interface. Over the past few years, the MOS (metal-oxide-semiconductor) approach has been highly developed and is the principal tool for the investigation of silicon surface phenomena. The theory of the ideal MOS capacitor is reviewed followed by a study of its use in the analysis of surface effects. Finally, the three-way relationship of the effect of oxide formation conditions and heat treatment on the properties of the oxidized silicon surface, and the subsequent influence of the properties of this surface on semiconductor device parameters is reviewed.     

The effect of thermal-neutron radiation on the decomposition of an oxygen solid solution in silicon

This paper presents the analysis of peculiarities of defect formation in the course of thermal treatment in silicon single crystals grown by the Czochralski method and exposed to thermal-neutron radiation, under the modes usually applied in transmutation doping of silicon ingots. The processes of defect formation were estimated using X-ray diffuse scattering and IR-spectroscopy. It is demonstrated that such doping results in the variation of the state in the material lattice of impurities such as oxygen and carbon. Moreover, subsequent high-temperature annealing leads to the recovery of concentration of interstitial oxygen and does not result in the recovery of the carbon concentration in the lattice nodes. The effect is studied of radiation on peculiar features of the formation of oxygen-containing microdefects in a silicon lattice at high-temperature annealing, used for the formation of an internal getter in silicon wafers.     

Integration of screen-printing and rapid thermal processingtechnologies for silicon solar cell fabrication

For the first time, the potentially cost-effective technologies of rapid thermal processing (RTP) and screen-printing (SP) have been combined into a single process sequence to achieve solar cell efficiencies as high as 14.7% on 0.2 Ω-cm FZ and 14.8% on 3 Ω-cm Cz silicon. These results were achieved without application of a nonhomogeneous (selective) emitter, texturing, or oxide passivation. By tailoring the RTP thermal cycles for emitter diffusion and firing of the screen-printed silver contacts, fill factor values >0.79 were realized on emitters with a sheet resistance (ρ_s ) of ~20 Ω/□ and grid shading <6%. Such high fill factors clearly demonstrate that screen-printed contacts can be fired on extremely shallow RTP emitters (x_j=0.25-0.3 μm) without shunting cells. IQE analysis depicts a strong preference for shallow emitter junction depths to achieve optimal short wavelength response of these unpassivated emitters. In some cases, front contacts were printed through plasma enhanced chemical vapor deposited (PECVD) SiN/SiO₂ dielectrics which prevented the shunting of shallow emitters by serving as partial barriers minimizing the diffusion of metallic species from the contacts. The firing of screen-printed contacts through these PECVD films, achieved the multiple purposes of contact formation, efficient front surface passivation due to annealing of the SiN, and high quality antireflection (AR). Research is presently underway to further optimize the RTP emitter design for screen-printing and develop techniques for implementing selective emitter and oxide passivation technologies for higher efficiency cells