富硅—氮化硅薄膜的PECVD制備及其退火處理研究
發(fā)布時間：2018-08-27 16:48
【摘要】：納米材料的量子限制效應(yīng)已在硅基納米材料及其發(fā)光機(jī)制方面深入研究。硅基發(fā)光材料中的硅量子點是由于量子限制效應(yīng)特性,而且量子點發(fā)光波長可隨量子點尺度變化,在光電子器件中具有非常好的應(yīng)用前景。將包含硅量子點的硅基材料逐漸引入到太陽能電池中。這樣可以使太陽光的有效吸收增強(qiáng),太陽電池的光電轉(zhuǎn)換效率提高,能成為未來高效的第三代硅量子點太陽能電池最有可能的競爭者�；谶@些優(yōu)點,本論文利用等離子體增強(qiáng)化學(xué)氣相沉積(PECVD)法制備富硅-氮化硅薄膜材料,研究沉積參數(shù)對富硅-氮化硅薄膜結(jié)構(gòu)的影響,以及制備薄膜后再進(jìn)行退火處理的發(fā)光特性質(zhì)的研究,有益于得出最佳的工藝參數(shù)應(yīng)用于材料的制備中。本文利用射頻PECVD法制備富硅SiN_x薄膜材料,此方法具有制備方法簡單、制備溫度低、沉積速率快、能量損失少,生產(chǎn)效率高等特點。對所沉積的薄膜樣品進(jìn)行X射線衍射、傅里葉變換紅外、光致發(fā)光、紫外可見光吸收譜等分析,對沉積條件在薄膜微結(jié)構(gòu)、結(jié)晶情況、組分含量、發(fā)光特性等方面的影響進(jìn)行研究,制備出氮化硅及富硅氮化硅薄膜,然后對富硅氮化硅薄膜進(jìn)行后續(xù)退火處理。本論文實驗研究結(jié)果分為如下幾個部分:1.反應(yīng)氣源為SiH_4、NH_3、N_2,文章研究N_2流量的改變對制備氮化硅薄膜結(jié)構(gòu)及性質(zhì)的影響。實驗結(jié)果分析表明:少量通入氮流量,薄膜Si-N鍵濃度增強(qiáng),氮與硅含量比值增大;繼續(xù)增加氮流量,薄膜逐漸呈富氮態(tài),伴隨缺陷態(tài)增多,輻射增強(qiáng),光學(xué)帶隙迅速展寬,帶尾態(tài)能量逐漸減小;氮含量較高時,形成了包埋在非晶SiN_x母質(zhì)中的Si3N4晶粒,且晶粒逐漸增加,實現(xiàn)了從非晶SiN_x到包含Si3N4小晶粒的薄膜材料的演變過程。2.反應(yīng)氣源為SiH_4、NH_3和H_2,文章研究NH_3流量的改變對制備富硅-氮化硅薄膜材料的影響。實驗結(jié)果分析表明:氨氣流量增加,N原子和H原子數(shù)量增多,Si-H鍵和Si-N振動強(qiáng)度逐漸增強(qiáng)。當(dāng)?shù)雍枯^高時,容易形成N的懸掛鍵,而高電負(fù)性的N影響Si-H鍵電子云的分布且向高波數(shù)方向發(fā)生一定的藍(lán)移,同時薄膜樣品本身存有大量的結(jié)構(gòu)缺陷。而光學(xué)帶隙關(guān)聯(lián)于薄膜中的缺陷態(tài)密度,缺陷越多,光學(xué)帶隙越寬。隨著氨氣流量不斷的增加,氫原子飽和多余的懸掛鍵,有益于硅氮鍵、硅氫鍵的形成,薄膜內(nèi)各化學(xué)鍵密度和各原子密度均有單調(diào)遞增的現(xiàn)象,Si/N原子比在0.903與0.994之間變化,薄膜逐漸成富硅-氮化硅材料。3.反應(yīng)氣源為SiH_4、NH_3、H_2,采用等離子體化學(xué)氣相沉積技術(shù)低溫沉積富硅-氮化硅薄膜,并置于退火爐內(nèi)對樣品熱退火處理,退火溫度為500℃、700℃和950℃,退火時間為90分鐘。實驗結(jié)果表明,700℃高溫退火后,薄膜中Si-H鍵和N-H鍵完全斷裂,H溢出薄膜。Si-H鍵的斷裂產(chǎn)生大量的硅懸掛鍵,N-H鍵的斷裂與周圍硅原子結(jié)合成Si-N鍵,使薄膜內(nèi)Si-N鍵增多,同時該峰亦逐漸向高波數(shù)方向移動,通過RBM模型分析表明硅原子鍵合氮原子數(shù)目增多,而薄膜的硅氮比值固定,導(dǎo)致薄膜有更多硅析出。在510-550nm處出現(xiàn)由硅量子點的限制效應(yīng)引起的發(fā)光帶,而薄膜內(nèi)的缺陷態(tài)復(fù)合引起了P1,P2,P3,P5四個發(fā)光峰的出現(xiàn)。分析了硅量子點隨退火溫度的生長導(dǎo)致P4發(fā)光峰紅移與藍(lán)移。隨著熱退火溫度增加,硅量子點的Raman峰逐漸向500cm-1靠近并計算出700℃和950℃溫度退火下樣品中硅量子點尺寸分別為3.01nm、3.05nm。
[Abstract]:Quantum confinement effect of nanomaterials has been studied in detail in silicon-based nanomaterials and their luminescent mechanism.Silicon quantum dots in silicon-based luminescent materials are due to their quantum confinement effect characteristics and the luminescent wavelength of quantum dots can vary with the size of quantum dots.Silicon containing silicon quantum dots has a very good application prospect in optoelectronic devices. Based on these advantages, plasma enhanced chemical vapor deposition (PECVD) is used to fabricate solar cells in this paper. Silicon-rich silicon nitride thin films were prepared, and the effects of deposition parameters on the structure of silicon-rich silicon nitride thin films were studied. The luminescent properties of silicon-rich silicon nitride thin films prepared by annealing were also studied. The optimum process parameters were obtained for the preparation of silicon-rich silicon nitride thin films. The preparation method is simple, the preparation temperature is low, the deposition rate is fast, the energy loss is small, and the production efficiency is high. Silicon nitride and silicon-rich silicon nitride thin films were prepared, and then silicon-rich silicon nitride thin films were annealed. The experimental results were divided into the following parts: 1. The reaction gas source was SiH_4, NH_3, N_2. The effect of N_2 flow rate on the structure and properties of silicon nitride thin films was studied. With the increase of nitrogen flow rate, the Si-N bond concentration and the ratio of nitrogen to silicon content of the films increase; with the increase of nitrogen flow rate, the films become nitrogen-rich gradually, and with the increase of defect state, the radiation increases, the optical band gap widens rapidly, and the band tail energy decreases gradually; when the nitrogen content is high, the Si_3N_4 grains embedded in the amorphous SiN_x parent material are formed, and the grains increase gradually. In addition, the evolution process from amorphous SiN x to thin film materials containing small Si3N4 grains is realized. 2. The reaction gas sources are SiH_4, NH_3 and H_2. The influence of NH_3 flow rate on the preparation of Si-rich silicon nitride thin film materials is studied. The experimental results show that the number of N atoms and H atoms increases with the increase of ammonia flow rate, and the vibration intensity of Si-H bonds and Si-N gradually increases. When the content of nitrogen atom is high, the suspended bond of N is easily formed, and the high electronegativity of N affects the distribution of electron cloud of Si-H bond and blue shift to high wavenumber. At the same time, there are a lot of structural defects in the film itself. The optical band gap is related to the density of defect states in the film, the more defects, the wider the optical band gap. With the increase of gas flow rate, hydrogen atom saturates the superfluous hanging bond, which is beneficial to the formation of silicon-nitrogen bond and silicon-hydrogen bond. The density of each chemical bond and each atom in the film increases monotonously. The Si/N atom ratio varies between 0.903 and 0.994, and the film gradually becomes silicon-rich silicon-nitride material. 3. Reaction gas source is SiH_4, NH_3, H_2, using plasma. Silicon-rich silicon nitride thin films were deposited by bulk chemical vapor deposition at low temperatures and annealed in an annealing furnace. The annealing temperatures were 500, 700 and 950, and the annealing time was 90 minutes. The breakage of N-H bond and Si-N bond make Si-N bond increase in the film, and the peak shifts to higher wave number. The RBM model analysis shows that the number of nitrogen atoms bonded by Si atoms increases, while the Si-N ratio of the film is fixed, resulting in more silicon precipitation in the film. Silicon quantum dots appear at 510-550 nm. Four luminescent peaks, P1, P2, P3 and P5, were induced by the recombination of defect states in the films. The red shift and blue shift of P4 luminescent peaks were analyzed with the growth of Si quantum dots at annealing temperature. The size of silicon quantum dots in the samples is 3.01nm, 3.05nm.
【學(xué)位授予單位】：內(nèi)蒙古師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O484
本文編號：2207856
[Abstract]:Quantum confinement effect of nanomaterials has been studied in detail in silicon-based nanomaterials and their luminescent mechanism.Silicon quantum dots in silicon-based luminescent materials are due to their quantum confinement effect characteristics and the luminescent wavelength of quantum dots can vary with the size of quantum dots.Silicon containing silicon quantum dots has a very good application prospect in optoelectronic devices. Based on these advantages, plasma enhanced chemical vapor deposition (PECVD) is used to fabricate solar cells in this paper. Silicon-rich silicon nitride thin films were prepared, and the effects of deposition parameters on the structure of silicon-rich silicon nitride thin films were studied. The luminescent properties of silicon-rich silicon nitride thin films prepared by annealing were also studied. The optimum process parameters were obtained for the preparation of silicon-rich silicon nitride thin films. The preparation method is simple, the preparation temperature is low, the deposition rate is fast, the energy loss is small, and the production efficiency is high. Silicon nitride and silicon-rich silicon nitride thin films were prepared, and then silicon-rich silicon nitride thin films were annealed. The experimental results were divided into the following parts: 1. The reaction gas source was SiH_4, NH_3, N_2. The effect of N_2 flow rate on the structure and properties of silicon nitride thin films was studied. With the increase of nitrogen flow rate, the Si-N bond concentration and the ratio of nitrogen to silicon content of the films increase; with the increase of nitrogen flow rate, the films become nitrogen-rich gradually, and with the increase of defect state, the radiation increases, the optical band gap widens rapidly, and the band tail energy decreases gradually; when the nitrogen content is high, the Si_3N_4 grains embedded in the amorphous SiN_x parent material are formed, and the grains increase gradually. In addition, the evolution process from amorphous SiN x to thin film materials containing small Si3N4 grains is realized. 2. The reaction gas sources are SiH_4, NH_3 and H_2. The influence of NH_3 flow rate on the preparation of Si-rich silicon nitride thin film materials is studied. The experimental results show that the number of N atoms and H atoms increases with the increase of ammonia flow rate, and the vibration intensity of Si-H bonds and Si-N gradually increases. When the content of nitrogen atom is high, the suspended bond of N is easily formed, and the high electronegativity of N affects the distribution of electron cloud of Si-H bond and blue shift to high wavenumber. At the same time, there are a lot of structural defects in the film itself. The optical band gap is related to the density of defect states in the film, the more defects, the wider the optical band gap. With the increase of gas flow rate, hydrogen atom saturates the superfluous hanging bond, which is beneficial to the formation of silicon-nitrogen bond and silicon-hydrogen bond. The density of each chemical bond and each atom in the film increases monotonously. The Si/N atom ratio varies between 0.903 and 0.994, and the film gradually becomes silicon-rich silicon-nitride material. 3. Reaction gas source is SiH_4, NH_3, H_2, using plasma. Silicon-rich silicon nitride thin films were deposited by bulk chemical vapor deposition at low temperatures and annealed in an annealing furnace. The annealing temperatures were 500, 700 and 950, and the annealing time was 90 minutes. The breakage of N-H bond and Si-N bond make Si-N bond increase in the film, and the peak shifts to higher wave number. The RBM model analysis shows that the number of nitrogen atoms bonded by Si atoms increases, while the Si-N ratio of the film is fixed, resulting in more silicon precipitation in the film. Silicon quantum dots appear at 510-550 nm. Four luminescent peaks, P1, P2, P3 and P5, were induced by the recombination of defect states in the films. The red shift and blue shift of P4 luminescent peaks were analyzed with the growth of Si quantum dots at annealing temperature. The size of silicon quantum dots in the samples is 3.01nm, 3.05nm.
【學(xué)位授予單位】：內(nèi)蒙古師范大學(xué)
【學(xué)位級別】：碩士
【學(xué)位授予年份】：2017
【分類號】：O484
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