Wet cleaning and surface characterization of Si1−xGex virtual substrates after a CMP step

New reactants such as ozone dissolved in ultra-pure water have been widely used the last few years instead of the original Radio Corporation of America (RCA) cleaning (which is a combination of the Standard Cleaning 1 (SC1) and the Standard Cleaning 2 (SC2)). In a first part of the study (Microelectron. Eng. 83 (2006) 1986), we had quantified the efficiency of a new cleaning sequence (that calls upon HF and H₂O/O₃ solutions) on polished Si_1−xGe_x virtual substrates (x = 0.2-0.5). We are discussing here the surface morphology and wetability together with the oxide thickness and structure typically obtained after this so-called “DDC-SiGe” wet cleaning. Flat surface morphologies are found after cleaning whatever the Ge content (from 20 to 50%). Typical root mean square roughness is around 0.4 nm. We have used X-ray Photoelectron Spectroscopy to determine the characteristics of the surface termination after this “DDC-SiGe” cleaning. An oxide mainly composed of SiO₂ is formed, with a low fraction of Ge sub-oxide and GeO₂. The distribution of chemical species is not that different from the one obtained after the use of a SC1 cleaning. However, the chemical oxide formed is slightly thicker. Such a HF/O₃ cleaning leads, when used on thick Ge layers grown on Si, to the formation of a really thin Ge sub-oxide. Our oxidation model assumes a competition in O₃ solutions between the oxidation rates of Si and Ge atoms (faster for Si) and the dissolution of the Ge oxide formed in solution. This mechanism, which implies the formation of a slightly porous oxide, is different from the one seeming to occur in SC1-based solutions. Indeed, the addition of surfactant in a SC1 solution modifies the oxidation rate compared to standard SC1 or O₃-based solutions, suggesting a diffusion of reactants towards the interface between the SiGe and the oxide in formation, assisted by the reactions of species within the cleaning solutions.     

Effect of temperature and silicon resistivity on the elaboration of silicon nanowires by electroless etching

The morphology of silicon nanowire (SiNW) layers formed by Ag-assisted electroless etching in HF/H₂O₂ solution was studied. Prior to the etching, the Ag nanoparticles were deposited on p-type Si(1 0 0) wafers by electroless metal deposition (EMD) in HF/AgNO₃ solution at room temperature. The effect of etching temperature and silicon resistivity on the formation process of nanowires was studied. The secondary ion mass spectra (SIMS) technique is used to study the penetration of silver in the etched layers. The morphology of etched layers was investigated by scanning electron microscope (SEM).     

Mechanism of atomic-scale passivation and flattening of semiconductor surfaces by wet-chemical preparations

Atomic arrangements of Si(001), Si(110) and 4H-SiC(0001) surfaces after wet-chemical preparations are investigated with scanning tunneling microscopy. Their passivated structures as well as the surface formation mechanisms in aqueous solutions are discussed. On both Si(001) and Si(110) surfaces, simple 1 × 1 phases terminated by H atoms are clearly resolved after dilute HF dipping. Subsequent etching with water produces the surfaces with 'near-atomic' smoothness. The mechanisms of atomic-scale preferential etching in water are described in detail together with first-principles calculations. Furthermore, 4H-SiC(0001), which is a hard material and where it is difficult to control the surface structure by solutions, is flattened on the atomic scale with Pt as a catalyst in HF solution. After a mechanism is proposed based on electroless oxidation, the flattened surface mainly composed of a 1 × 1 phase is analyzed. The obtained results will be helpful from various scientific and technological viewpoints.     

Arc plasma jet cleaning of the silicon surface before CoSi2/Si contact formation

Cleaning of the silicon surface before Co film deposition is a key procedure in the synthesis of silicide (CoSi₂) and, hence, in the production of the metal-semiconductor contact. This study deals with a new method of surface cleaning using arc plasma jet treatment (APJT) at atmospheric pressure. The results show that cleaning of the Si surface using APJT (Ar/CCIF₃) improves the Schottky barrier contact parameters in comparison with conventional wet HF final cleaning and additional cleaning using in situ Ar-ion-beam sputter etching. Moreover, substantially longer time of wafer exposure to air between final cleaning and metal deposition is acceptable. Auger electron spectroscopy shows that APJT removes oxygen from the Si surface.     

Study of the structural perfection and distribution/redistribution of silicon in epitaxial GaAs films grown by molecular beam epitaxy on (100), (111)A, and (111)B substrates

Silicon distribution before and after thermal annealing in thin doped GaAs layers grown by molecular beam epitaxy on (100)-, (111)A-, (111)B-oriented substrates is studied by X-ray diffraction and SIMS. The surface morphology of the epitaxial films inside and outside an ion etch crater that arises during SIMS measurements is studied by atomic force microscopy. Distinctions in the surface relief inside the crater for different orientations have been revealed. Observed differences in the doping profiles are explained by features of the surface relief developing in the course of ion etching in SIMS measurements and by enhanced Si diffusion via growth defects.     

Hydrogen on Si: Ubiquitous surface termination after wet-chemical processing

The manufacture of microelectronic devices based on silicon technology is largely dominated by wet chemical processes. By ultraclean sample preparation in air and a fast transfer into UltraHigh Vacuum (UHV) we open up a way for the atomic-scale structural and chemical characterization of silicon surfaces immediately after wet-chemical processing. Using Scanning Tunneling Microscopy (STM), ThermoDesorption (TDS) and InfraRed Spectroscopy (IRS), we find that a surface termination predominantly by hydrogen results from all the different wet-chemical treatments investigated (etching with hydrofluoric acid, rinsing with hot water, chemomechanical polishing)-despite the different chemical ambients and process parameters involved. Microscopically, a crystallographically preferential attack of the silicon is observed in all these processes which results, to a different extent, in anisotropic defect structures on the surfaces. This is explained by an interplay of aqueous reaction kinetics and sterical hindrance on the silicon surface. It is pointed out how a UHV surface analysis of the micromorphology of wet-chemically treated silicon surfaces, so far carried out mostly on Si(111) due to its easier preparation and experimental accessability, may help to provide the in-depth understanding of the atomic-scale mechanisms during wet-chemical processing demanded by the progressing miniaturization of microelectronic devices. The atomically smoother and chemically more homogeneous Si(111) obtained after preferential etching with NH₄F suggests that in future applications Si(111) may gain importance over Si(100), which still dominates in today's semiconductor technology, since future devices increasingly rely on tailor-made and ideal properties on an atomic scale. Due to their structural and chemical simplicity and well-controlable characteristics, H-teminated surfaces after wet-chemical preparation also form ideal substrates for conventional UHV surface studies such as absorption and MBE-growth experiments.     

Investigation of native-oxide growth on HF-treated Si(111) surfaces by measuring the surface-state distribution

The evaluation of the surface state distribution of differently HF-treated Si(111) surfaces during the native-oxide growth in air is investigated by the large-signal field-modulated photovoltage technique. The surface state distribution consisting of intrinsic and extrinsic Si dangling bond defects is directly related to the state of oxidation of the Si surface. It is shown that the kind of HF treatment strongly influences the concentration of extrinsic defects with a lower state of oxidation. Special HF preparations for H termination of the Si(111) surface result in a nearly intrinsic surface state distribution. During the oxidation process three typical phases can be distinguished each characterized by specific defect structures. It was found that native-oxide growth is highly sensitive to the concentration of extrinsic defects directly after HF treatment.     

Modifying of etching anisotropy of silicon substrates by surface active agents

The influence of alcohol additives on etch rate anisotropy of Si(hkl) planes has been studied. The etching processes were carried out in 3 and 5 M KOH aqueous solutions saturated and non-saturated with alcohols. Isopropanol, 1-propanol and tert-butanol were examined. It has been showed that the etching process cannot be controlled only by the surface tension of the solution. Saturation of the etching solution with alcohols modifies etch rate anisotropy, lowering the ratio of the etch rate of (110) and vicinal planes to the etch rate of (100) plane. The morphology of Si(hkl) planes etched in 3 M KOH solution saturated with tert-butyl alcohol has been studied in detail. Smooth (331) and (221) planes have been achieved in this solution. The (100) plane turned out to be densely covered by hillocks, opposite to the (100) plane etched in weak-alkaline solution saturated with isopropanol. To explain this phenomenon, the mechanism of hillocks formation on Si(100) surface has been proposed.     

Structural and optical properties of thin films porous amorphous silicon carbide formed by Ag-assisted photochemical etching

In this work, we present the formation of porous layers on hydrogenated amorphous SiC (a-SiC: H) by Ag-assisted photochemical etching using HF/K₂S₂O₈ solution under UV illumination at 254 nm wavelength. The amorphous films a-SiC: H were elaborated by d.c. magnetron sputtering using a hot pressed polycrystalline 6H-SiC target. Because of the high resistivity of the SiC layer, around 1.6 MΩ cm and in order to facilitate the chemical etching, a thin metallic film of high purity silver (Ag) has been deposited under vacuum onto the thin a-SiC: H layer. The etched surface was characterized by scanning electron microscopy, secondary ion mass spectroscopy, infrared spectroscopy and photoluminescence. The results show that the morphology of etched a-SiC: H surface evolves with etching time. For an etching time of 20 min the surface presents a hemispherical crater, indicating that the porous SiC layer is perforated. Photoluminescence characterization of etched a-SiC: H samples for 20 min shows a high and an intense blue PL, whereas it has been shown that the PL decreases for higher etching time. Finally, a dissolution mechanism of the silicon carbide in 1HF/1K₂S₂O₈ solution has been proposed.     

Stability of hydrogen-terminated vicinal Si(1 1 1) surface under ambient atmosphere

In this paper a comparative study of different wet-chemical etching procedures of vicinal Si(1 1 1) surface passivation is presented. The stability against oxidation under ambient atmosphere was studied by X-ray photoelectron spectroscopy and atomic force microscopy. The best results were achieved by the buffered HF etching and the final smoothing of the surface by hot (72 °C) NH₄F. The procedures consisting of a large number of etching steps were unsatisfactory, since the probability of contamination during each step was increasing. The passivated surface was stable against oxidation for at least 3 h under ambient atmosphere.     

Formation of aligned silicon nanowire on silicon by electroless etching in HF solution

It was demonstrated that the etching in HF-based aqueous solution containing AgNO₃ and Na₂S₂O₈ as oxidizing agents or by Au-assisted electroless etching in HF/H₂O₂ solution at 50 °C yields films composed of aligned Si nanowire (SiNW). SiNW of diameters ∼10 nm were formed. The morphology and the photoluminescence (PL) of the etched layer as a function of etching solution composition were studied. The SiNW layers formed on silicon were investigated by scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) and photoluminescence. It was demonstrated that the morphology and the photoluminescence of the etched layers strongly depends on the type of etching solution. Finally, a discussion on the formation process of the silicon nanowires is presented.     

Passivation of structured p-type silicon interfaces: Effect of surface morphology and wet-chemical pre-treatment

The effect of both surface morphology and wet-chemical pre-treatment on electronic surface and interface properties was investigated for mono- and polycrystalline silicon substrates with special surface structures. Surface charge, energetic distribution, and density of rechargeable states on these surfaces were determined by surface photovoltage (SPV) measurements. These results were correlated to previously reported findings on atomically flat Si(111) and Si(100) surfaces of monocrystalline wafers. In this paper, a specially optimised sequence of cleaning, wet-chemical oxidation, and oxide removal procedures is described in detail for the first time. This method was successfully applied in order to remove contaminations and damaged surface layers and to obtain atomically flat areas on substrates with evenly distributed atomic steps, polycrystalline and monocrystalline substrates with randomly distributed pyramids. A significant reduction in surface micro-roughness, interface state density, and recombination loss was achieved. Using passivation by wet-chemical oxidation or H-termination, respectively, the optimised surface state can be preserved by the time of following preparation steps and during subsequent a-Si:H plasma enhanced chemical vapour deposition (PECVD).     

KrF-excimer-laser-induced native oxide removal from Si (100) surfaces studied by Auger electron spectroscopy

The mechanism of KrF-excimer-laser cleaning of Si(100) surfaces was studied by Auger Electron Spectroscopy (AES) and Low-Energy Electron Diffraction (LEED) spectroscopy. The dependence of the cleaning efficiency on the laser fluence was investigated by using a mildly focused laser beam and carefully measuring the energy density distribution of the laser spot impinging on the sample. These values were compared with the AES spectra measured in different points of the irradiated area and with the morphology observed by optical microscopy. Samples as received from the manufacturer were first investigated. It was found that desorption of weakly bonded organic adsorbates occurs at energy densities as low as 0.3 J/cm², whereas significant oxide removal takes place only at an energy density above 0.8 J/cm², which produces damaged surface morphologies. The experimental findings, in agreement with the temperatures calculated for the laser-induced Si heating, indicated that a large fraction of the oxide film is dissolved in the molten silicon, leading to oxygen concentration below the AES detection limit only when the melted depth was of the order of several hundred nanometers. Atomically clean, damage-free Si(100) surfaces were obtained after irradiation of samples pre-etched for 1 min in a HF: H₂O (5%) solution, which had only a thin SiO _x (x < 2) layer and F, C and O containing adsorbed species. Complete contaminant elimination was achieved in this case with 15 pulses at 0.8 J/cm² without any damaging of the surface.     

Wet-chemical passivation of atomically flat and structured silicon substrates for solar cell application

Special sequences of wet-chemical oxidation and etching steps were optimised with respect to the etching behaviour of differently oriented silicon to prepare very smooth silicon interfaces with excellent electronic properties on mono- and poly-crystalline substrates. Surface photovoltage (SPV) and photoluminescence (PL) measurements, atomic force microscopy (AFM) and scanning electron microscopy (SEM) investigations were utilised to develop wet-chemical smoothing procedures for atomically flat and structured surfaces, respectively. Hydrogen-termination as well as passivation by wet-chemical oxides were used to inhibit surface contamination and native oxidation during the technological processing. Compared to conventional pre-treatments, significantly lower micro-roughness and densities of surface states were achieved on mono-crystalline Si(100), on evenly distributed atomic steps, such as on vicinal Si(111), on silicon wafers with randomly distributed upside pyramids, and on poly-crystalline EFG (Edge-defined Film-fed-Growth) silicon substrates.The recombination loss at a-Si:H/c-Si interfaces prepared on c-Si substrates with randomly distributed upside pyramids was markedly reduced by an optimised wet-chemical smoothing procedure, as determined by PL measurements. For amorphous-crystalline hetero-junction solar cells (ZnO/a-Si:H(n)/c-Si(p)/Al) with textured c-Si substrates the smoothening procedure results in a significant increase of short circuit current I_sc, fill factor and efficiency η. The scatter in the cell parameters for measurements on different cells is much narrower, as compared to conventional pre-treatments, indicating more well-defined and reproducible surface conditions prior to a-Si:H emitter deposition and/or a higher stability of the c-Si surface against variations in the a-Si:H deposition conditions.     

Chemical etching investigation of polycrystalline p-type 6H-SiC in HF/Na2O2 solutions

In this work, an experimental study on the chemical etching reaction of polycrystalline p-type 6H-SiC was carried out in HF/Na₂O₂ solutions. The morphology of the etched surface was examined with varying Na₂O₂ concentration, etching time, agitation speed and temperature. The surfaces of the etched samples were analyzed using scanning electron microscopy (SEM), energy-dispersive X-ray (EDX) Fourier transform infrared spectroscopy (FT-IR) and photoluminescence. The surface morphology of samples etched in HF/Na₂O₂ is shown to depend on the solution composition and bath temperature. The investigation of the HF/Na₂O₂ solutions on 6H-SiC surface shows that as Na₂O₂ concentration increases, the etch rate increases to reach a maximum value at about 0.5 M and then decreases. A similar behaviour has been observed when temperature of the solution is increased. The maximum etch rate is found for 80 °C. In addition, a new polishing etching solution of 6H-SiC has been developed. This result is very interesting since to date no chemical polishing solution has been developed on the material.     

多晶硅表面酸腐蚀制备绒面研究

采用各向同性腐蚀法制备多晶硅绒面,腐蚀液为HF和HNO3的混合溶液,缓和剂为NaH2PO4.2H2O溶液.利用SEM、AFM和紫外分光光度计对硅片绒面进行检测和分析,初步探讨了酸腐蚀机理.结果表明:采用NaH2PO4.2H2O溶液作为缓和剂,腐蚀后的硅片表面具有均匀的腐蚀坑,表面陷光效果较好,通过优化各种参量,反应速度可以控制在2 μm/min左右,适合工业生产的要求.在富HF时,硅片表面易形成尖锐边缘的腐蚀坑,出现或多或少的小孔,反射率最低可达16.5%～17.5%|在富HNO3时,硅片表面易形成腐蚀坑较浅、尺寸偏大的气泡状绒面或光面,反射率较高.     

The contribution of surface effects to the surface photovoltage dependence on temperature for the real Si(111) surface

The dependences of the surface photovoltage and photoconductivity on temperature (in the range of 300–430 K) for the real p- and n-type Si(111) surface have been measured. The results of the experiments have shown the strong influence of the surface treatment (etching in HF solution or baking in vacuum) on the temperature dependences of the surface photovoltage and photoconductivity. Good qualitative agreement has been obtained between experimental and theoretical plots of the surface photovoltage as a function of temperature calculated on the basis of the Lile theory.     

The changes in morphology of Si(1 0 0) surface upon dipping in ultrapure water

The changes in morphology and chemical states of Si(1 0 0) surface upon dipping in ultrapure water were investigated by using atomic force microscope and X-ray photoelectron spectroscopy. The oxidation and the etching competitively progressed at the HF-treated Si(1 0 0) surface in ultrapure water, which made the smooth surface rough. However, the surface covered with a thick native oxide film was not etched at all. During the repetition of the oxidation and the etching, the SiO₂-nuclei was, by chance, able to grow up to some size of islands and worked as the protective barrier against the water etching. Thus, the SiO₂-islands would remain without being etched off, whereas rest parts of the surface could be etched off. This selective etching leads the surface morphology to become rough. Both the oxidation and the etching progressed violently as the water temperature and the dipping time increased.     

AFM measurement of atomic-scale Si surface etching by active oxidation

Atomic-scale etching of a clean Si surface by active oxidation with oxygen molecules was examined using ex-situ atomic force microscopy (AFM). The etch rate was directly determined by measuring the etch depth with AFM. A SiO₂ anti-etching mask was used on a H-terminated Si(001)-2 × 1:H surface prepared by low pH HF treatment followed by annealing in H₂. The etch rate under active oxidation conditions was almost proportional to the O₂ pressure, which was consistent with previous reports. The etch rate exhibited a weak temperature dependence with an apparent activation energy of 0.2 eV. A distinct transition of the reaction mode from etching to oxide formation was observed in detail as an abrupt decrease of the etch rate by lowering the temperature near the boundary condition between the etching and oxide formation conditions.     

HF酸腐蚀提高K9基板损伤阈值

针对K9玻璃基板的HF酸化学腐蚀工艺开展研究,标定了40%和2%高低两种体积分数的HF酸的腐蚀速率;分析了基板表面形貌随腐蚀深度的变化规律;研究了腐蚀时间、HF酸体积分数、超声波工艺对激光损伤阈值的影响,提出了能够有效减少损伤敏感的氟硅盐沉淀、提高损伤阈值的优化腐蚀清洗工艺流程。采用优化的腐蚀清洗工艺流程进行了实验验证,结果表明用体积分数为2%的HF酸在高温和超声波条件下腐蚀90s后,测得1064nm波长激光作用下K9基板抗激光损伤阈值提高了75%。