Spectroscopic diagnostics of temperature-controlled trench etching of silicon

Ernission from the plasma species CCl, CN, CO, N₂, and Si was monitored during trench etching of silicon with a CHCl,₃/ N, chemistry. The temperature of the backside of the wafer was recorded simultaneously. The emission response to experimentally induced perturbations of the plasma was found to be particularly informative. One such perturbation was a sudden change of the wafer temperature through control of the He pressure under the wafer. The other perturbation involved a drastic change of the N₂, flow rate. Our results confirm the mechanism of control of the trench profile through the temperature-dependent rate of deposition of polymers on the sidewalls during etch. Further, N₂, which certainly plays a crucial role in this chemistry, may engage in a surface reaction producing CN radicals; our data are consistent with this surface reaction. Finally, an algorithm was constructed for real-time monitoring of the selectivity of .silicon to the oxide mask; selectivity is shown to be very sensitive to the presence of N₂.     

Mechanism of silicon film deposition in the RF plasma reduction of silicon tetrachloride

Plasma-chemical reduction of SiCl₄ in mixtures with H₂ and Ar has been studied by optical emission spectroscopy (OES) and laser interferometry techniques. It has been found that the Ar:H₂ ratio strongly affects the plasma composition as well as the deposition (r _D) and etch (r _E) rates of Si: H, Cl films and that the electron impact dissociation is the most important channel for the production of SiCl_x species, which are the precursors of the film growth. Chemisorption of SiCl_x and the reactive surface reaction SiCl_x+H–SiCl_(x–1)0+HCl are important steps in the deposition process. The suggested deposition model givesr _D [SiCl_x][H], in agreement with the experimental data. Etching of Si: H, Cl films occurs at high Ar: H₂ ratio when Cl atoms in the gas phase become appreciable and increases with increasing Cl concentration. The etch rate is controlled by the Cl atom chemisorption step.     

Spectroscopic diagnostics of temperature-controlled trench etching of silicon

Emission from the plasma species CCI, CN, CO, N₂, and Si teas monitored during trench etching of silicon with a CHCl₃/ N, chernistrv. The temperature of the backside of the wafer was recorded simultaneously. The emission response to experimentally induced perturbations of the plasma was found to be particularly informative. One such perturbation teas a sudden change of the wafer temperature through control of the He pressure under the wafer. The other perturbation involved a drastic change of the N₂ flow rate. Our results confirm the mechanism of control of the trench profile through the temperature-dependent rate of deposition of polymers on the sidewalls during etch. Further, N₂, which certainly plays a crucial role in this chemistry, may engage in a surlàce reaction producing CN radicals; our data are consistent with this surlàce reaction. Finally, an algorithm tvas constructed for real-time monitoring of the selectivity of .silicon to the oxide mask; selectivity is shown to be very sensitive to the presence of N₂.     

Adsorption and surface diffusion of silicon growth species in silicon carbide chemical vapour deposition processes studied by quantum-chemical computations

The effect chlorine addition to the gas mixture has on the surface chemistry in the chemical vapour deposition (CVD) process for silicon carbide (SiC) epitaxial layers is studied by quantum-chemical calculations of the adsorption and diffusion of SiH₂ and SiCl₂ on the (000-1) 4H–SiC surface. SiH₂ was found to bind more strongly to the surface than SiCl₂ by approximately 100 kJ mol^?1 and to have a 50 kJ mol^?1 lower energy barrier for diffusion on the fully hydrogen-terminated surface. On a bare SiC surface, without hydrogen termination, the SiCl₂ molecule has a somewhat lower energy barrier for diffusion. SiCl₂ is found to require a higher activation energy for desorption once chemisorbed, compared to the SiH₂ molecule. Gibbs free energy calculations also indicate that the SiC surface may not be fully hydrogen terminated at CVD conditions since missing neighbouring pair of surface hydrogens is found to be a likely type of defect on a hydrogen-terminated SiC surface.     

Direct Spectroscopic Evidence of the Influence of Chamber Wall Condition on Oxide Etch Rate

The drift of TEOS etch rate has been observed during MERIE oxide etch for the damascene process. The etch rate typically fluctuates between 5300 Å/min and 6000 Å/min. Studies using fluorocarbon-based chemistry show a normal TEOS etch rate when the chamber wall is heavily coated with polymer deposition. On the other hand, a lower etch rate appears when the chamber has less deposition. Hysteresis behavior has been observed during the etch rate of TEOS, as well as emission intensity trends of F, CF _x (x=1~3), and SiF. From the observed emission intensity variation of F, CF _x , and SiF, a model is proposed to explain the impact of chamber wall polymer deposition on the etch rate of TEOS. This model includes a mechanism of etch rate enhancement by embedding oxygen in the chamber wall polymer. From the correlation between etch rate and emission intensity, it clearly shows that F is directly responsible for the etch of TEOS. Compared to F, CF _x plasma chemistry has a closer link to chamber wall polymer formation, but contributes less in the etch of TEOS.     

Products of thermal desorption from silicon after its prior reaction with hydrogen chloride

Conclusions After the prior reaction of silicon with hydrogen chloride the intermediate products that are formed on the silicon surface react among themselves, with the formation of SiCl₄, when the silicon is heated in the absence of HCl.Deceased.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No.2, pp.444–445, February, 1973.     

Optical Diagnostics of the Effect of Oxygen on Bi-Level Contact Etch

The effect of oxygen flow rate on bi-level contact etch was studied by observing uv-visible emission from the plasma, during CHF₃/CO/O₂ etching of di-electric layers consisting of SiO₂ and SiN_x. The emission intensity of CN at 387 nm drifted progressively from wafer to wafer during plasma etch. Such a phenomenon became more obvious when using low or high oxygen flow rate, whereas for intermediate flow rates, no significant drift of emission intensity was observed. The critical dimension (CD) bias of each wafer showed a strong correlation with CN emission intensity. Possible mechanisms for such an intensity drift phenomenon are proposed. The drift of emission intensity indicates that the contribution of chamber wall polymers in wafer etching is non-negligible. The CN emission intensity is an indication of the magnitude of etching rate. Our results suggest that the variation of plasma emission intensity might be used as an index for in-line monitoring of CD bias fluctuation.     

Surface effects on the diagnostic of carbon/nitrogen low‐pressure plasmas studied by differentially pumped mass spectrometry

In this work, the characterization of the species produced in reactive plasmas by differentially pumped mass spectrometry is addressed. A H₂/CH₄/N₂ mixture (90 : 5 : 5) was fed into a direct current glow discharge and analysed by conventional and cryo‐trap assisted mass spectrometry. The gaseous mixture was chosen because of its particular relevance in the inhibition of tritium‐rich carbon film deposition in fusion plasmas (scavenger technique) and in the deposition of amorphous hydrogenated carbon films by plasma‐assisted chemical vapour deposition. Important changes in the composition of the detected species upon surface modification of the reactor walls (stainless steel or covered by an amorphous hydrogenated carbon layer) or in the way they are sampled (length and spatial configuration of the stainless steel duct) were detected. They are analysed in terms of radical formation and recombination on the reactor walls or into the sampling duct, thus providing some insight into the underlying chemistry. In general, when the reactor walls are covered by an amorphous hydrogenated carbon layer, more hydrocarbons are produced, but the radical production is lower and seem to be less reactive than in stainless steel. Also, two sources of oxygen contamination in the plasma have been identified, from the native oxide layer in stainless steel and from unintended water contamination in the chamber, which modify considerably the detected species. Copyright © 2014 John Wiley & Sons, Ltd.     

Biocompatible "click" wafer bonding for microfluidic devices

We introduce a novel dry wafer bonding concept designed for permanent attachment of micromolded polymer structures to surface functionalized silicon substrates. The method, designed for simultaneous fabrication of many lab-on-chip devices, utilizes a chemically reactive polymer microfluidic structure, which rapidly bonds to a functionalized substrate via"click" chemistry reactions. The microfluidic structure consists of an off-stoichiometry thiol-ene (OSTE) polymer with a very high density of surface bound thiol groups and the substrate is a silicon wafer that has been functionalized with common bio-linker molecules. We demonstrate here void free, and low temperature (< 37 °C) bonding of a batch of OSTE microfluidic layers to a silane functionalized silicon wafer.     

Etching of Silicon Nitride in CCl2F2, CHF3, SiF4, and SF6 Reactive Plasma: A Comparative Study

Silicon nitride is an important material layer in various types of microelectronic devices. Because of continuous integration of devices, patterning of this layer requires a highly selective and anisotropic etching process. Reactive ion etching is one of the most simple and popular plasma processes. The present work is an experimental analysis of primary etch characteristics in reactive ion etching of silicon nitride using chlorine- and/or fluorine-based organic and inorganic chemistries (CCl ₂ F ₂+O ₂ , CHF ₃+O ₂ , SiF ₄ +O₂, SF₆+O ₂ , and SF ₆+He) in order to obtain a simultaneous etch selectivity against polysilicon and silicon dioxide. A recipe, in CCl ₂ F ₂ /O ₂ plasma chemistry, which provides acceptable etch characteristics, along with a reasonable simultaneous selectivity against polysilicon and silicon dioxide, has been formulated.     

Effect of Wafer Temperature on High Aspect Ratio Hardmask Etching

Fluorocarbon-based chemistries were used to study the effect of wafer temperature on the etch of high aspect ratio hardmasks composed of SiO₂ and SiN_x layers. It is found that etch stop can occur easily at high temperature. The rate of polymer deposition plays an important role in etch stop. The etching rates were found to be inversely proportional to the wafer temperature. Such a relation indicates a negative activation energy in the rate expression of hardmask etching using fluorocarbon plasma. It also implies that in hardmask etching, complicated gas-surface, but not simple one-step, reactions are involved. Different wafer surface temperature can provide different degree of activation for etching reactions. Analysis of etching rate and optical emission trends indicates that CF_x may contribute more than F does in the etch of SiO₂ and SiN_x, since polymer-rich etching chemistries were used. Based on the temperature-dependent etching rate, we propose a reaction mechanism for the reaction trends observed in hardmask etching.     

Chemical analysis of acidic silicon etch solutions: II. Determination of HNO3, HF, and H2SiF6 by ion chromatography

The processing of silicon in microelectronics and photovoltaics involves the isotropic chemical etching using HF-HNO₃ mixtures to clean the surface from contaminations, to remove the saw damage, as well as to polish or to texture the wafer surface. Key element of an effective etch process control is the knowledge of the actual etch bath composition in order to maintain a certain etch rate by replenishment of the consumed acids. The present paper describes a methods for the total analysis of the etch bath constituents HF, HNO₃, and H₂SiF₆ by ion chromatography. First step is the measurement of the total fluoride and nitrate content in the analyte. In a second step, H₂SiF₆ is precipitated as K₂SiF₆. After careful filtration of the precipitate, the fluoride concentration in the filtrate is measured and the content of free HF is calculated therefrom. The K₂SiF₆ is dissolved again and the fluoride content measured and recalculated as H₂SiF₆. The results obtained with the presented method are discussed with respect to the results from two other, previously published methods, based on a titration using methanolic cyclohexylamine solution as titrant and based on a method using a fluoride ion selective electrode (F-ISE). An evaluation with respect to the needs for an industrial application is given.     

Study of reactive ion etching of Si and SiO2 for CFxCl4−x gases

A parametric study of the etching of Si and SiO₂ by reactive ion etching (RIE) was carried out to gain a better understanding of the etching mechanisms. The following fluorocarbons (FCs) were used in order to study the effect of the F-to-Cl atom ratio in the parent molecule to the plasma and the etching properties: CF₄, CF₃Cl, CF₂Cl₂, and CFCl₃ (FC-14, FC-13, FC-12, and FC-11 respectively). The Si etch rate uniformity across the wafer as a function of the temperature of the wafer and the Si load, the optical emission as a function of the temperature of the load, the etch rate of SiO₂ as a function of the sheath voltage, and the mass spectra for each of the FCs were measured. The temperature of the wafer and that of the surrounding Si load strongly influence the etch rate of Si, the uniformity of etching, and the optical emission of F, Cl, and CF₂. The activation energy for the etching reaction of Si during CF₄ RIE was measured. The etch rate of Si depends more strongly on the gas composition than on the sheath voltage; it seems to be dominated by ion-assisted chemical etching. The etching of photoresist shifted from chemical etching to ion-assisted chemical etching as a function of the F-to-Cl ratio and the sheath voltage. The etch rate of SiO₂ depended more strongly on the sheath voltage than on the F-to-Cl ratio.     

A Comparative Study of HBr-Ar and HBr-Cl<Subscript>2</Subscript> Plasma Chemistries for Dry Etch Applications

The effects of HBr/Ar and HBr/Cl₂ mixing ratios in the ranges of 0–100% Ar or Cl₂ on plasma parameters, densities of active species influencing the dry etch mechanisms were analyzed at fixed total gas flow rate of 40 sccm, total gas pressure of 6 mTorr, input power of 700 W and bias power of 300 W. The investigation combined plasma diagnostics by Langmuir probes and the 0-dimensional plasma modeling. It was found that the dilution of HBr by Ar results in maximum effect on the ion energy flux with expected impact on the etch rate in the ion-flux-limited etch regime, while the addition of Cl₂ influences mainly the relative fluxes of Br and Cl atoms on the etched surface with expected impact on the etch rate in the reaction-rate-limited etch regime.     

Reactive species generated during wet chemical etching of silicon in HF/HNO3 mixtures

The role of intermediate species generated during wet chemical etching of silicon in a HF-rich HF/HNO3 mixture was studied by spectroscopic and analytical methods at 1 degrees C. The intermediate N2O3 was identified by its cobalt blue color and the characteristic features in its UV-vis and Raman spectra. Furthermore, a complex N(III) species (3NO+.NO3-) denoted as [N4O6(2+)] is observed in these solutions. The time-dependent decay of the N(III) intermediates, mainly by their oxidation at the liquid-air interface, serves as a precondition for the study of the etch rate as function of the intermediate concentration measured by Raman spectroscopy. From a linear relationship between etch rate and [N4O6(2+)] concentration, NO+ is considered to be a reactive species in the rate-limiting step. This step is attributed to the oxidation of permanent existing Si-H bonds at the silicon surface by the reactive NO+ species. N2O3 serves as a reservoir for the generation of NO+ leading to a complete coverage of the silicon surface with reactive species at high intermediate concentrations. As long as this condition is valid (plateau region), the etch rate is constant and yields a smooth silicon surface upon completion of the etching. If the N2O3 concentration is insufficient to ensure a coverage of the Si surface by NO+, the etch rate decreases linearly with the N2O3 concentration and results in a roughening of the etched silicon surface (slope region).     

A Disilene Base Adduct with a Dative Si–Si Single Bond

An experimental and theoretical study of the base‐stabilized disilene 1 is reported, which forms at low temperatures in the disproportionation reaction of Si₂Cl₆ or neo‐Si₅Cl₁₂ with equimolar amounts of NMe₂Et. Single‐crystal X‐ray diffraction and quantum‐chemical bonding analysis disclose an unprecedented structure in silicon chemistry featuring a dative Si→Si single bond between two silylene moieties, Me₂EtN→SiCl₂→Si(SiCl₃)₂. The central ambiphilic SiCl₂ group is linked by dative bonds to the amine donor and the bis(trichlorosilyl)silylene acceptor, which leads to push–pull stabilization. Based on experimental and theoretical examinations a formation mechanism is presented that involves an autocatalytic reaction of the intermediately formed anion Si(SiCl₃)₃^? with neo‐Si₅Cl₁₂ to yield 1 .     

Unraveling the Amine‐Induced Disproportionation Reaction of Perchlorinated Silanes—A DFT Study

A detailed quantum‐chemical study on the amine‐induced disproportionation reaction of perchlorinated silanes to neo‐Si₅Cl₁₂ is reported. The key intermediate in the resulting mechanistic scenario is a dichlorosilylene amine adduct, which is in tune with recent experimental findings. Yet, at variance with the generally accepted notion of silicon‐chain growth by concerted silylene insertion into Si?Cl bonds of lower silanes, the formation of neo‐Si₅Cl₁₂ follows more complex pathways. The reactivity is dominated by the Lewis–base character of the dichlorosilylene amine adduct and characterized by three elementary steps that bear close resemblance to the key elementary steps identified earlier for the chloride‐induced disproportionation of Si₂Cl₆. NBO and QTAIM analyses of the key reactive species SiCl₂ ? NMe₃ and SiCl₃^? provide a rationale for these striking similarities.     

Behavior of carbon-containing impurities during plasma synthesis of trichlorosilane

The behavior of CCl₄ and CHCl₃ admixtures during the plasma synthesis of trichlorosilane via the hydrogenation of SiCl₄ in a capacitively coupled radiofrequency (40.68 MHz) discharge was studied. It was shown that the main portion of the impurities undergo chemical transformations yielding silicon carbide and carbon. The degree of conversion determined from the impurity concentrations in the reactant SiCl₄ and its hydrogenation products is strongly dependent on the processing parameters and reaches 99.9% for CCl₄ and 96% for CHCl₃.     

NHC→SiCl4: An Ambivalent Carbene‐Transfer Reagent

The addition of BCl₃ to the carbene‐transfer reagent NHC→SiCl₄ (NHC=1,3‐dimethylimidazolidin‐2‐ylidene) gave the tetra‐ and pentacoordinate trichlorosilicon(IV) cations [(NHC)SiCl₃]⁺ and [(NHC)₂SiCl₃]⁺ with tetrachloroborate as counterion. This is in contrast to previous reactions, in which NHC→SiCl₄ served as a transfer reagent for the NHC ligand. The addition of BF₃ ? OEt₂, on the other hand, gave NHC→BF₃ as the product of NHC transfer. In addition, the highly Lewis acidic bis(pentafluoroethyl)silane (C₂F₅)₂SiCl₂ was treated with NHC→SiCl₄. In acetonitrile, the cationic silicon(IV) complexes [(NHC)SiCl₃]⁺ and [(NHC)₂SiCl₃]⁺ were detected with [(C₂F₅)SiCl₃]^? as counterion. A similar result was already reported for the reaction of NHC→SiCl₄ with (C₂F₅)₂SiH₂, which gave [(NHC)₂SiCl₂H][(C₂F₅)SiCl₃]. If the reaction medium was changed to dichloromethane, the products of carbene transfer, NHC→Si(C₂F₅)₂Cl₂ and NHC→Si(C₂F₅)₂ClH, respectively, were obtained instead. The formation of the latter species is a result of chloride/hydride metathesis. These compounds may serve as valuable precursors for electron‐poor silylenes. Furthermore, the reactivity of NHC→SiCl₄ towards phosphines is discussed. The carbene complex NHC→PCl₃ shows similar reactivity to NHC→SiCl₄, and may even serve as a carbene‐transfer reagent as well.     

Orientation of Antibodies on a 3-Aminopropyltriethoxylsilane-Modified Silicon Wafer Surface

An antibody can be specifically oxidized with periodate (NaIO₄) on the carbohydrate side chains at its C-terminal. Rabbit anti-hepatitis B surface antigen (anti-HBsAg) IgG antibodies were bound to the silicon wafer surface by covalent bonds between aldehydes generated on the carbohydrate side chains of the antibodies and the reactive amine groups of 3-aminopropyltriethoxylsilane(APTES)-modified silicon wafer surfaces. A control experiment was also performed by direct attachment of antibodies to glutaraldehyde-treated silicon surfaces. Two different coupling antibody strategies were investigated in this paper. Atomic force microscopy was used to observe the orientation of the site-directed and random attachment of rabbit anti-HBsAg IgG antibodies and the conservation of their antigen-binding capacity (AgBC) was assessed using an enzyme immunoassay (EIA).