本文選題：吸氣劑薄膜 + 直流磁控濺射　； 參考：《北京有色金屬研究總院》2016年博士論文

【摘要】：吸氣劑是一種通過物理和化學作用吸收活性氣體來維持和提升電真空器件的真空品質(zhì)的特殊功能材料。隨著電真空器件的微型化與集成化,對維持其可靠性、穩(wěn)定性和長壽命的吸氣劑技術(shù)提出了新的挑戰(zhàn)。傳統(tǒng)吸氣元件由于體積大且需要高溫激活,已很難在MEMS真空封裝器件中直接應(yīng)用,薄膜型吸氣劑作為有效的解決方案受到了真空科學與技術(shù)業(yè)界的廣泛關(guān)注。國外在真空封裝用吸氣劑薄膜領(lǐng)域的研究工作開展相對較早,在學術(shù)研究和工程應(yīng)用方面均有較大進展。我國目前在真空封裝用吸氣劑薄膜方面的研究工作開展相對較少,具有自主知識產(chǎn)權(quán)的吸氣劑薄膜技術(shù)與產(chǎn)品還鮮有報道,因此加強我國在該技術(shù)領(lǐng)域的自主創(chuàng)新研究工作具有重要的學術(shù)和工程意義。本文以Zr-Co-Ce吸氣合金作為研究對象,采用磁控濺射法沉積了Zr-Co-Ce吸氣劑薄膜,研究了影響薄膜結(jié)構(gòu)和性能的關(guān)鍵工藝環(huán)節(jié),探索了優(yōu)化薄膜吸氣性能的有效途徑,并通過對薄膜激活過程研究,分析探討了薄膜的激活機理,最后對薄膜的實用性能進行了評測。具體研究工作和主要結(jié)論如下:(1)采用磁控濺射技術(shù)在Si襯底上沉積了多孔ZrCoCe吸氣劑薄膜,探討了工作電源模式、襯底溫度、濺射氣壓、沉積掠射角、工作氣體流量等工藝參數(shù)對薄膜結(jié)構(gòu)及吸氣性能的影響。研究發(fā)現(xiàn),直流(DC)磁控濺射較之射頻(RF)磁控濺射更有利于制備多孔柱狀結(jié)構(gòu)ZrCoCe薄膜。襯底溫度和濺射氣壓對薄膜的微觀組織結(jié)構(gòu)影響較為顯著,相對較高的襯底溫度和濺射氣壓更有利于獲得多孔柱狀結(jié)構(gòu)的薄膜。隨著沉積掠射角的增大,沉積過程中的原子陰影效應(yīng)增大,薄膜的柱狀組織隨之增多。隨著Ar氣體流量的增大,薄膜的沉積速率增大,表面晶粒排列無序度隨之增加,薄膜容易獲得較高的比表面積。在襯底溫度150℃、濺射氣壓3 Pa、掠射角70°、Ar氣體流量45 sccm的工藝條件下制備ZrCoCe吸氣劑薄膜獲得了相對理想的吸氣性能,300℃激活30min后對H2的初始吸附速率達到238 cm3·s-1·cm-2。(2)研究了襯底除氣工藝對薄膜最終吸氣性能的影響,結(jié)果表明襯底吸附的殘余活性氣體是導致薄膜激活過程中發(fā)生毒化的重要原因。設(shè)計并制備了在結(jié)構(gòu)上分別具有阻擋層和保護層的ZrCoCe吸氣劑薄膜,并研究了膜層結(jié)構(gòu)對薄膜微觀組織與吸氣性能的影響。研究結(jié)果顯示,預沉積于襯底表面的一層致密阻擋層,可以有效降低襯底殘氣導致的毒化效應(yīng),同時也有利于提高吸氣薄膜的比表面積,獲得更佳的吸氣性能。沉積于薄膜表面的Ni保護層,能夠有效降低ZrCoCe薄膜的表面氧化程度,改善薄膜的吸氣性能。(3)基于MEMS真空封裝的工藝特點,對所制備的ZrCoCe薄膜進行了實用性評測,主要研究了激活溫度和重復激活對薄膜微觀結(jié)構(gòu)和吸氣性能的影響,并對薄膜的抗清洗溶劑毒化和大氣氧化能力進行了考察。結(jié)果表明,ZrCoCe薄膜可在300~400℃溫度范圍加熱保溫30 min實現(xiàn)激活。較低激活溫度主要導致薄膜表面鈍化層的還原,薄膜晶態(tài)結(jié)構(gòu)變化不大,吸氣性能相對較低;較高激活溫度不僅能改變薄膜表面化學活性狀態(tài),還會影響其微觀晶態(tài)結(jié)構(gòu),兩者協(xié)同作用使得薄膜吸氣性能獲得大幅提升。經(jīng)異丙醇和Ar+等離子體清洗處理后,ZrCoCe薄膜初始吸氣速率分別提高了23%和57%。薄膜吸氣性能隨暴露大氣時間的延長而呈現(xiàn)明顯衰減趨勢,暴露時間越久,性能衰減越嚴重。暴露大氣時間超過50天后,薄膜初始吸氣速率降至沉積態(tài)薄膜的30.6%。(4)首次結(jié)合XPS分析、四極質(zhì)譜分析(QMS)及熱力學計算對ZrCoCe薄膜的激活過程進行了研究,探討了ZrCoCe薄膜的激活機理,為設(shè)計低溫激活吸氣劑薄膜提供了理論依據(jù)。研究發(fā)現(xiàn),暴露過大氣的ZrCoCe薄膜表面覆蓋著H2O、CO2和碳氫化合物等,薄膜表面的Zr和Ce主要以氧化態(tài)存在,而Co則主要以低價態(tài)氫氧化物的形式存在。在薄膜的加熱激活過程中,Zr的氧化物在300℃開始還原;激活過程還導致了薄膜表面金屬態(tài)鈷的偏析及亞表面鋯的碳化物的生成。隨著激活溫度的升高,薄膜表面吸附態(tài)的H2O、CO2和碳氫化合物等氣體逐漸發(fā)生脫附,200℃以上的主要脫附氣體為H2,整個激活過程未發(fā)現(xiàn)脫附的O2;金屬氧化物中的O主要以向薄膜內(nèi)部擴散的方式而離開薄膜表面,從而實現(xiàn)氧化態(tài)向金屬態(tài)或近金屬態(tài)的轉(zhuǎn)變。
[Abstract]:The absorbant is a special functional material for maintaining and improving the vacuum quality of an electric vacuum device by absorbing active gases by physical and chemical effects. With the miniaturization and integration of an electric vacuum device, a new challenge is put forward for the technology to maintain its reliability, stability and long life. It is difficult to be used directly in the MEMS vacuum packaging device. The film type suction agent is widely concerned in the vacuum science and technology industry as an effective solution. The research work in the field of vacuum packaging in the field of vacuum packaging is relatively early, and great progress has been made in the field of academic research and engineering applications. At present, there are relatively few research work in the field of vacuum packaging in our country, and there are few reports on the technology and products of the aspirant film with independent intellectual property rights. Therefore, it is of great significance to strengthen our own research on independent innovation in this field. This paper is based on Zr-Co-Ce suction alloy as research research. The Zr-Co-Ce getter film was deposited by magnetron sputtering. The key process factors affecting the structure and properties of the film were studied. The effective way to optimize the performance of the film was explored. The activation mechanism of the film was studied and the practical performance of the film was evaluated. The main research work and main conclusions are as follows: (1) a porous ZrCoCe getter film was deposited on Si substrate by magnetron sputtering. The influence of working power mode, substrate temperature, sputtering pressure, deposition angle, working gas flow rate on the structure and suction performance of the film was discussed. The study found that the DC (DC) magnetron sputtering was more than the sputtering. The frequency (RF) magnetron sputtering is more conducive to the preparation of a porous columnar structure ZrCoCe film. The influence of substrate temperature and sputtering pressure on the microstructure of the thin films is more significant. The relatively high substrate temperature and sputtering pressure are more favorable for obtaining a porous columnar structure film. With the increase of the deposition angle and the atomic shadow effect in the deposition process With the increase of the Ar gas flow, the deposition rate of the film increases, the disordering of the surface grains increases, and the thin film easily obtains a higher specific surface area. The ZrCoCe getter film is prepared under the substrate temperature of 150 C, the sputtering pressure of 3 Pa, the grazing angle 70 degrees, and the Ar gas flow rate of 45 SCCM The relatively ideal suction performance was obtained. The initial adsorption rate of H2 at 300 C was reached to 238 cm3. S-1. Cm-2. (2). The effect of the substrate degassing process on the final gas absorption properties of the film was studied. The results showed that the residual active gas adsorbed by the substrate was an important cause of the toxicity of the film during the activation process. The effect of the membrane structure on the microstructure and the suction performance of the film is studied in the structure of the ZrCoCe. The results show that a dense barrier layer deposited on the substrate surface can effectively reduce the toxic effect of the substrate residual gas and also improve the ratio of the absorption film to the substrate. The Ni protection layer deposited on the surface of the film can effectively reduce the surface oxidation of the ZrCoCe film and improve the gas absorption performance of the film. (3) based on the technological characteristics of the MEMS vacuum packaging, the practical measurement of the prepared ZrCoCe film is carried out, and the activation temperature and the reactivation of the film are mainly studied. The effects of microstructures and inspiratory properties were investigated, and the anti cleaning solvent toxicity and atmospheric oxidation ability of the film were investigated. The results showed that the ZrCoCe film could be activated at 30 min at the temperature range of 300~400 C. The lower activation temperature was the main cause of the passivation layer on the film surface. The higher activation temperature can not only change the chemical activity state of the film surface, but also influence the microstructure of the film. The synergism of the two causes the film absorption performance to be greatly improved. After the isopropanol and Ar+ plasma cleaning, the initial gas absorption rate of the ZrCoCe film increases by 23% and the 57%. film absorption performance with the storm, respectively. The longer the exposure time shows the obvious attenuation trend, the longer the exposure time, the worse the performance attenuation. The initial suction rate of the film to the deposited film is reduced to 30.6%. (4) 30.6%. (4) for the first time, and the activation process of ZrCoCe film is studied by quadrupole mass spectrometry (QMS) and thermodynamic calculation. The activation mechanism of the ZrCoCe film provides a theoretical basis for the design of the active absorption film at low temperature. It is found that the surface of the ZrCoCe film exposed to the atmosphere is covered with H2O, CO2 and hydrocarbons. The Zr and Ce on the surface of the film mainly exist in the oxidation state, while the Co is mainly in the form of low valence hydroxide. During the living process, the oxide of Zr begins to reduce at 300. The activation process also leads to the segregation of cobalt on the surface of the film and the formation of the carbides of the subsurface zirconium. With the increase of the activation temperature, the adsorbed H2O, CO2 and hydrocarbon of the film surface gradually degenerate, and the main desorption gas above 200 c is the whole activation. The O2 is not found in the process, and the O in the metal oxide leaves the surface of the film mainly in the way of diffusion in the film, so as to realize the transition from the oxidation state to the metal state or the near metal state.
【學位授予單位】：北京有色金屬研究總院
【學位級別】：博士
【學位授予年份】：2016
【分類號】：TB383.2

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