Etching of quartz crystals in liquid phase environment:A review

Quartz crystals are the most widely used material in resonant sensors,owing to their excellent piezoelectric and mechanical properties.With the development of portable and wearable devices,higher processing efficiency and geometrical precision are required.Wet etching has been proven to be the most efficient etching method for large-scale production of quartz devices,and many wet etching approaches have been developed over the years.However,until now,there has been no systematic review of quartz crystal etching in liquid phase environments.Therefore,this article provides a comprehensive review of the development of wet etching processes and the achievements of the latest research in thisfield,covering conventional wet etching,additive etching,laser-induced backside wet etching,electrochemical etching,and electrochemical discharge machining.For each technique,a brief overview of its characteristics is provided,associated problems are described,and possible solutions are discussed.This review should provide an essential reference and guidance for the future development of processing strategies for the manufacture of quartz crystal devices.

Fabrication of Nanoscale Step Height Structure Using Atomic Layer Deposition Combined with Wet Etching

The current techniques used for the fabrication of nanosteps are normally done by layer growth and then ion beam thinning. There are also extra films grown on the step surfaces in order to reduce the roughness. So the whole process is time consuming. In this paper, a nanoscale step height structure is fabricated by atomic layer deposition （ALD） and wet etching techniques. According to the traceable of the step height value, the fabrication process is controllable. Because ALD technology can grow a variety of materials, aluminum oxide （Al2O3） is used to fabricate the nanostep. There are three steps of Al2O3 in this structure including 8 nm, 18 nm and 44 inn. The thickness of Al2O3 film and the height of the step are measured by anellipsometer. The experimental results show that the thickness of Al2O3 film is consistent with the height of the step. The height of the step is measured by AFM. The measurement results show that the height is related to the number of cycles of ALD and the wet etching time. The bottom and the sidewall surface roughness are related to the wet etching time. The step height is calibrated by Physikaliseh-Technische Bundesanstalt （PTB） and the results were 7.5±1.5 nm, 15.5±2.0 nm and 41.8±2.1 nm, respectively. This research provides a method for the fabrication of step height at nanoscale and the nanostep fabricated is potential used for standard references.

Improvement in a-plane GaN crystalline quality using wet etching method

Nonpolar （1120） GaN films are grown on the etched a-plane GaN substrates via metalorganic vapor phase epitaxy. High-resolution X-ray diffraction analysis shows great decreases in the full width at half maximum of the samples grown on etched substrates compared with those of the sample without etching, both on-axis and off-axis, indicating the reduced dislocation densities and improved crystalline quality of these samples. The spatial mapping of the E2 （high） phonon mode demonstrates the smaller line width with a black background in the wing region, which testifies the reduced dislocation densities and enhanced crystalline quality of the epitaxial lateral overgrowth areas. Raman scattering spectra of the E2 （high） peaks exhibit in-plane compressive stress for all the overgrowth samples, and the E2 （high） peaks of samples grown on etched substrates shift toward the lower frequency range, indicating the relaxations of in-plane stress in these GaN films. Furthermore, room temperature photoluminescence measurement demonstrates a significant decrease in the yellow-band emission intensity of a-plane GaN grown on etched templates, which also illustrates the better optical properties of these samples.

Six million Q factor micro fused silica shell resonator with teeth-like tines released by femtosecond laser-assisted chemical etching

The quality factor(Q factor)is a crucial performance parameter for resonators.In this paper,a novel release method for highquality micro fused silica shell resonators with teeth-like tines with good surface morphology is proposed.This method is based on femtosecond laser-assisted chemical etching.First,the optimal energy range of femtosecond laser modification is obtained through mechanism analysis.Second,the optimal parameters for a straight line and arc pattern are determined by optimizing the average output power,processing speed,and processing spacing.The results demonstrate why edge breakage in rounded corners is easy under different parameters.Finally,according to these conclusions,the processing is performed on a micro fused silica shell resonator with a Q factor exceeding 6 million.In addition,subsurface damage is rare throughout the fabrication process,and the surface roughness of the released cross section reaches the nanometer level.The improved Q factor helps suppress mechanical thermal noise and reduce zero bias and zero bias drift,constituting the primary method for enhancing the performance of the resonant gyroscope.

Fabrication of Diamond Microstructures by Using Dry and Wet Etching Methods

Diamond films have great potential for micro-electro-mechanical system（MEMS） application.For device realization,precise patterning of diamond films at micrometer scale is indispensable.In this paper,simple and facile methods will be demonstrated for smart patterning of diamond films,in which two etching techniques,i.e.,plasma dry etching and chemical wet etching（including isotropic-etching and anisotropic-etching） have been developed for obtaining diamond microstructures with different morphology demands.Free-standing diamond micro-gears and micro-combs were achieved as examples by using the experimental procedures.It is confirmed that as-designed diamond structures with a straight side wall and a distinct boundary can be fabricated effectively and efficiently by using such methods.

Investigation of chlorine-based etchants in wet and dry etching technology for an InP planar Gunn diode

Mesa etching technology is considerably important in the Gunn diode fabrication process. In this paper we fabricate InP Gunn diodes with two different kinds of chlorine-based etchants for the mesa etching for comparative study. We use two chlorine-based etchants, one is HCl-based solution （HC1/H3PO4）, and the other is Cl2-based gas mixture by utilizing inductively coupled plasma system （ICP）. The results show that the wet etching （HCl-based） offers low cost and approximately vertical sidewall, whilst ICP system （C12-based） offers an excellent and uniform vertical sidewall, and the over-etching is tiny on the top and the bottom of mesa. And the fabricated mesas of Gunn diodes have average etching rates of 0.6 p.m/min and 1.2 pm/min, respectively. The measured data show that the current of Gunn diode by wet etching is lower than that by ICP, and the former has a higher threshold voltage. It provides a low-cost and reliable method which is potentially applied to the fabrication of chip terahertz sources.

Wet etching and passivation of GaSb-based very long wavelength infrared detectors

The etching and passivation processes of very long wavelength infrared(VLWIR)detector based on the InAs/GaSb/AlSb type-II superlattice have been studied.By studying the effect of each component in the citric acid solution(citric acid,phosphoric acid,hydrogen peroxide,deionized water),the best solution ratio is obtained.After comparing different passivation materials such as sulfide+SiO_(2),Al_(2)O_(3),Si_(3)N_(4) and SU8,it is found that SU8 passivation can reduce the dark current of the device to a greater degree.Combining this wet etching and SU8 passivation,the of VLWIR detector with a mesa diameter of 500μm is about 3.6Ω·cm^(2) at 77 K.

Physical analysis of normally-off ALD Al_(2)O_(3)/GaN MOSFET with different substrates using self-terminating thermal oxidation-assisted wet etching technique

Based on the self-terminating thermal oxidation-assisted wet etching technique,two kinds of enhancement mode Al_(2)O_(3)/GaN MOSFETs(metal-oxide-semiconductor field-effect transistors)separately with sapphire substrate and Si sub-strate are prepared.It is found that the performance of sapphire substrate device is better than that of silicon substrate.Comparing these two devices,the maximum drain current of sapphire substrate device(401 mA/mm)is 1.76 times that of silicon substrate device(228 mA/mm),and the field-effect mobility(μ_(FEmax))of sapphire substrate device(176 cm^(2)/V·s)is 1.83 times that of silicon substrate device(96 cm^(2)/V·s).The conductive resistance of silicon substrate device is 21.2Ω-mm,while that of sapphire substrate device is only 15.2Ω·mm,which is 61%that of silicon substrate device.The significant difference in performance between sapphire substrate and Si substrate is related to the differences in interface and border trap near Al_(2)O_(3)/GaN interface.Experimental studies show that(i)interface/border trap density in the sapphire substrate device is one order of magnitude lower than in the Si substrate device,(ii)Both the border traps in Al_(2)O_(3) dielectric near Al_(2)O_(3)/GaN and the interface traps in Al_(2)O_(3)/GaN interface have a significantly effect on device channel mobility,and(iii)the properties of gallium nitride materials on different substrates are different due to wet etching.The research results in this work provide a reference for further optimizing the performances of silicon substrate devices.

Etching Behavior of GaN/GaAs(001) Epilayers Grown by MOVPE

Wet etching characteristics of cubic GaN (c GaN) thin films grown on GaAs(001) by metalorganic vapor phase epitaxy (MOVPE) are investigated.The samples are etched in HCl,H 3PO 4,KOH aqueous solutions,and molten KOH at temperatures in the range of 90～300℃.It is found that different solution produces different etch figure on the surfaces of a sample.KOH based solutions produce rectangular pits rather than square pits.The etch pits elongate in 1 0] direction,indicating asymmetric etching behavior in the two orthogonal <110> directions.An explanation based on relative reactivity of the various crystallographic planes is employed to interpret qualitatively the asymmetric etching behavior.In addition,it is found that KOH aqueous solution would be more suitable than molten KOH and the two acids for the evaluation of stacking faults in c GaN epilayers. direction,indicating asymmetric etching behavior in the two orthogonal <110> directions.An explanation based on relative reactivity of the various crystallographic planes is employed to interpret qualitatively the asymmetric etching behavior.In addition,it is found that KOH aqueous solution would be more suitable than molten KOH and the two acids for the evaluation of stacking faults in c GaN epilayers.

Etching‐assisted femtosecond laser modification of hard materials

With high hardness, high thermal and chemical stability and excellent optical performance, hard materials exhibit great potential applications in various fields, especially in harsh conditions. Femtosecond laser ablation has the capability to fabricate three-dimensional micro/nanostructures in hard materials. However, the low efficiency, low precision and high surface roughness are the main stumbling blocks for femtosecond laser processing of hard materials. So far, etching- assisted femtosecond laser modification has demonstrated to be the efficient strategy to solve the above problems when processing hard materials, including wet etching and dry etching. In this review, femtosecond laser modification that would influence the etching selectivity is introduced. The fundamental and recent applications of the two kinds of etching assisted femtosecond laser modification technologies are summarized. In addition, the challenges and application prospects of these technologies are discussed.

Enhanced etching of silicon didioxide guided by carbon nanotubes in HF solution

This paper describes a new method to create nanoscale SiO2 pits or channels using single-walled carbon nanotubes （SWNTs） in an HF solution at room temperature within a few seconds. Using aligned SWNT arrays, a pattern of nanoscale SiO2 channels can be prepared. The nanoscale SiO2 patterns can also be created on the surface of three- dimensional （3D） SiO2 substrate and even the nanoscale trenches can be constructed with arbitrary shapes. A possible mechanism for this enhanced etching of SiO2 has been qualitatively analysed using defects in SWNTs, combined with H3O＋ electric double layers around SWNTs in an HF solution.

Depth profiling of arsenian pyrite in Carlin-type ores through wet chemistry

Enrichment of As and Au at the overgrowth rims of arsenian pyrite is a distinctive feature of Carlin-type gold ores.Revealing distribution of such key elements in high resolution is of fundamental importance yet often proves challenging.In this study,repeated non-oxidative acid etching of ore samples from Shuiyindong gold deposit was applied to enable elemental depth profiling of goldbearing arsenian pyrite grains.ICP-OES and AAS were used to determine the dissolved Fe,As,and Au concentrations in each of the etching solutions,and XPS was carried out to exam the etched mineral surfaces.In contrast to conventional ion beam etching that may cause substantial sample damage,our acid etching method does not seem to significantly alter the composition and chemical state of the samples.The etched depths directly converted from the measured elemental concentrations can reproducibly reach a very high resolution of~1 nm,and can be conveniently controlled through varying the etching time.While the Fe and As depth profiles consistently reflect the surface oxidation property of arsenian pyrite,the Au profile displaying an obvious upward trend reveals the ore fluid evolution at the late stage of mineralization.Based on our experimental results,we demonstrate that our wet chemistry method is capable of effective depth profiling of gold ore and perhaps other geological samples,with advantages surpassing many instrumental techniques including negligible sample damage,nanoscale resolution as well as isotropic etching.

MEMS矢量水听器敏感结构的后CMOS释放工艺研究

纤毛式微机电系统(MEMS)矢量水听器可探测水下质点振速等矢量信息,与互补金属氧化物半导体(CMOS)集成能够很大程度地提升其性能。针对纤毛式MEMS矢量水听器的CMOS集成提出了一种方案,该方案在MEMS后处理工艺中,利用侧墙保护和各向异性湿法腐蚀从正面释放水听器的十字梁敏感结构。整个后处理过程不需要光刻,降低加工难度的同时,保证了加工结构的精确性。设计出了一种验证性的工艺流程,具体分析了4种不同结构的湿法腐蚀过程。最终完成了这4种结构的工艺流片,对实验结果进行了分析。实验验证了该方案的可行性,为纤毛式MEMS矢量水听器的CMOS集成奠定了基础。

湿法刻蚀条件对TFT中Cu电极坡度角和均一性的影响及工艺参数优化

目的 在高世代薄膜晶体管(Thin Film Transistor,TFT)产线的栅极刻蚀制程,明确大气压等离子体(Atmosphere Pressure Plasma,APP)清洗功率、清洗时间及刻蚀时间对刻蚀性能(关键尺寸偏差、均一性、坡度角)的影响规律,并获得最佳工艺条件,进而提升良率。方法 以APP清洗功率、清洗时间和刻蚀时间为影响因素,以关键尺寸偏差(CD Bias)、均一性、坡度角作为因变量,开展正交试验,明确因素影响重要性顺序;然后,对Cu电极坡度角的形成和刻蚀均一性变化进行分析;最后,采用回归分析获得刻蚀性能与刻蚀时间的函数关系式。结果 结果表明:刻蚀时间对刻蚀性能的影响最大,对APP清洁时间和功率的影响较小。刻蚀时间延长,关键尺寸偏差(CD Bias)增加、均一性变差、坡度角变大。为改善均一性和平缓坡度角,应缩短刻蚀时间。最佳工艺组合为:刻蚀时间85 s,APP电压9 kV,APP传输速度5 400 r/min。结论 刻蚀时间延长,未被光刻胶覆盖的Cu膜层被完全刻蚀,形成台阶,该台阶使刻蚀液形成回流路径。沿着回流路径,刻蚀液浓度、温度逐渐下降,刻蚀均一性由此恶化,坡度角因此增加。采用回归分析得到的刻蚀性能与刻蚀时间的函数关系式,为预测刻蚀效果和优选刻蚀时间提供了依据。

界面钻蚀主导的准各向异性湿法刻蚀法制备玻璃微棱镜阵列

玻璃微棱镜具有耐腐蚀、耐高温、寿命长等优点,但在玻璃上加工微棱镜阵列目前仍是一个难题。因此,提出了界面钻蚀主导的玻璃准各向异性湿法刻蚀方法,制备了高质量的微棱镜阵列器件。在元胞自动机中引入界面性质调控,模拟了界面钻蚀与各向同性侧蚀的竞争行为,探究了刻蚀横截面形貌的变化规律,构建了准各向异性湿法刻蚀模型。在此指导下,加工了横截面为梯形的微结构,设计并制备了间距、形状、尺寸均可调控的微棱镜阵列,重复性达到98%。验证了微棱镜阵列对LED灯扩散效果,光亮度提升了4.6倍。本文改变了传统玻璃湿法刻蚀各向同性的固有认识,创新性地开发了准各向异性刻蚀工艺,为玻璃微棱镜阵列等相关器件提供了高效低成本的制备方法。

InAs/GaSb超晶格台面刻蚀工艺研究综述

本文综述了InAs/GaSb超晶格台面刻蚀工艺研究。从湿法和干法刻蚀的物理化学机理以及参数调控等方面进行分析,旨在阐明工艺条件对台面形貌的影响,以抑制带隙较窄的长波和甚长波超晶格表面漏电流。结果表明,湿法刻蚀中恰当的腐蚀液配比可以实现两种组分的均匀性刻蚀,而不会导致粗糙的表面和严重的下切;干法刻蚀中,采用Cl_(2)基和CH 4基混合气体,通过调整刻蚀气体类型及比例可实现物理和化学刻蚀两个过程的平衡,保证台面侧壁平滑性和倾角的垂直度。另外,对于不同组分的超晶格,需要选择不同的工艺参数才能满足InAs和GaSb的协同性刻蚀。最后对InAs/GaSb超晶格台面刻蚀工艺作出了展望。

小闪耀角单晶硅光栅结构参数优化及制备工艺

本文开展了对单晶硅小闪耀角光栅的各向异性湿法刻蚀制备工艺研究,制备了适用于软X射线中波波段的闪耀光栅,以满足国家同步辐射光源的需要。首先,基于严格耦合波法对小闪耀角光栅进行了结构参数优化及工艺容差分析。在晶向对准过程中,先通过环形预刻蚀确定硅片晶向,再基于倍频调整法实现光栅掩模与单晶硅<111>晶向的对准。研究了光刻胶灰化技术及活性剂对光栅槽形质量的影响,并通过单晶硅各向异性湿法刻蚀工艺成功制备了接近于理想锯齿槽形的闪耀光栅。实验结果证明:所制备光栅闪耀角为1°,刻线密度为1200 gr/mm,闪耀面均方根粗糙度在0.5 nm以内。此方法可以应用于软X射线中波波段闪耀光栅的制作,在获得较高衍射效率的同时可以大大减少制作难度及成本。

Na_(2)O-CaO-SiO_(2)平板玻璃减反射功能化研究

随着光伏产业的高速发展,与之配套使用的减反射玻璃重新进入了研究者们的视野。本文采用湿化学二步刻蚀法制备了具有减反射性能的Na_(2)O-CaO-SiO_(2)平板玻璃,采用分光光度计、扫描电子显微镜、原子力显微镜和X射线能谱仪等测试样品的透过率、表面形貌和断面膜层厚度、表面化学成分、耐酸性和硬度,研究了反应温度和反应时间、玻璃膜层结构与透过率的关系。通过使用弱碱性的混合盐溶液对Na_(2)O-CaO-SiO_(2)玻璃表面进行化学刻蚀,使玻璃表面Si—O键断裂,在玻璃表面形成纳米膜层结构,当膜层厚度达到一定厚度时,一定波长的光在玻璃表面发生相消干涉,透过率最高可达到97.8%,刻蚀前后玻璃成分基本无变化,铅笔硬度达到3H。

石英湿法腐蚀及谐振器制作工艺研究

随着石英谐振器向小型化、高频化发展,其尺寸越来越小,因此,低成本的谐振器精准制造工艺尤为重要。该文对石英晶片进行腐蚀实验以确定精准制造矩形谐振器的最佳工艺条件,研究了温度对金属保护层完整性的影响,以及腐蚀时间对石英表面粗糙度的影响。腐蚀速率稳定且适中,有利于谐振器的精准制造。设计了石英谐振器工艺流程,得到质量较好的超薄矩形AT切高频石英谐振器。分析其尺寸误差产生的原因,并总结了一套精度较好的湿法腐蚀工艺,有望采用低成本手段使矩形谐振器的厚度小于10μm。

基于仿生蛾眼结构制备减反射微晶玻璃

目的采用湿法刻蚀制备减反射微晶玻璃,分析晶化时间对透过率、反射率和形貌的影响。方法通过熔融法制备得到基础玻璃,调整晶化时间制备得到一系列不同晶粒尺寸(12.2~27.4nm)的微晶玻璃,将制备得到的基础玻璃及不同晶粒尺寸的微晶玻璃放置在配制好的5%(质量分数)HF、2%(质量分数)SiO_(2)、1.5%(质量分数)BaSO_(4)、2%(质量分数)羧甲基纤维素钠、89.5%(质量分数)H_(2)O的刻蚀液中,在25℃条件下,以40 kHz的超声频率双面蚀刻60 min,通过分光光度计测试刻蚀前后样品的透过率和反射率,利用扫描电子显微镜对刻蚀前后样品的表面和断面形貌进行表征。结果基础玻璃在500℃核化230 min,665℃晶化135 min后,制备得到微晶玻璃的晶粒尺寸约为25.1 nm,进一步经过湿法刻蚀后,刻蚀深度约为150 nm,蛾眼玻璃透过率最高为98.02%。结论微晶玻璃经过湿法刻蚀后增透效果明显,对X射线衍射(XRD)、掠入射X射线衍射(GIXRD)、扫描电子显微镜(SEM)的测试结果进行分析可知,微晶玻璃中存在晶体相和残余玻璃相,经过酸蚀处理后,表面能形成以透锂长石晶体和二硅酸锂晶体均匀分布的蛾眼结构,晶体尺寸为12.2~27.4 nm的微晶玻璃进行湿法刻蚀后透过率分布在95.99%~98.02%。