技术领域technical field
本发明涉及多晶硅薄膜材料的制备领域，具体而言，涉及一种多晶硅薄膜材料的制备方法。The invention relates to the field of preparation of polysilicon thin film materials, in particular to a preparation method of polysilicon thin film materials.
背景技术Background technique
多晶硅薄膜材料由于具有原材料丰富、便于大面积沉积、光电性能优异、载流子迁移率高等优势而广泛地应用于太阳能电池、薄膜场效应晶体管等领域。目前常用的多晶硅薄膜材料的制备方法可分为两大类，一是直接沉积法，一般是利用化学气相沉积技术，包括等离子增强化学气相沉积(PECVD)、低压化学气相沉积(LPCVD)、热丝化学气相沉积(HWCVD)，在600℃以上的温度，利用硅烷等反应气体直接在衬底上沉积多晶硅薄膜。这类直接沉积的方法由于温度较高，所以不能以廉价的玻璃作为衬底，限制了其发展。Polycrystalline silicon thin film materials are widely used in solar cells, thin film field effect transistors and other fields due to their advantages such as abundant raw materials, easy large-area deposition, excellent photoelectric performance, and high carrier mobility. At present, the commonly used preparation methods of polysilicon thin film materials can be divided into two categories, one is the direct deposition method, generally using chemical vapor deposition technology, including plasma enhanced chemical vapor deposition (PECVD), low pressure chemical vapor deposition (LPCVD), hot wire Chemical vapor deposition (HWCVD), at a temperature above 600°C, uses reactive gases such as silane to directly deposit polysilicon films on the substrate. Due to the high temperature of this direct deposition method, cheap glass cannot be used as a substrate, which limits its development.
另一类就是间接法，主要包括：固相晶化技术(SPC)、快速热退火技术(RTA)、金属诱导晶化技术(MIC)、激光诱导晶化技术(LIC)。这类方法的共同特点是先在低温下沉积非晶硅薄膜，然后使其再结晶。其中SPC技术和RTA技术在再结晶的过程中仍需使用600℃以上的高温，因此仍有衬底的限制。MIC技术是一种低温晶化技术，是通过在非晶硅薄膜的表面或底部沉积一层金属膜来降低晶化温度，这种技术的优势是可使用廉价的玻璃衬底，且能耗低。存在的问题是所需的金属层往往较厚，如有很多研究显示非晶硅薄膜与金属铝膜的厚度之比大于2:1时才能达到金属诱导晶化的效果，因此金属污染问题是该技术的一个瓶颈。The other is the indirect method, mainly including: solid phase crystallization (SPC), rapid thermal annealing (RTA), metal-induced crystallization (MIC), and laser-induced crystallization (LIC). The common feature of these methods is to deposit an amorphous silicon film at low temperature and then recrystallize it. Among them, SPC technology and RTA technology still need to use a high temperature above 600°C in the process of recrystallization, so there is still a limitation of the substrate. MIC technology is a low-temperature crystallization technology, which reduces the crystallization temperature by depositing a metal film on the surface or bottom of the amorphous silicon film. The advantage of this technology is that it can use cheap glass substrates and has low energy consumption. . The problem is that the required metal layer is often thick. For example, many studies have shown that the effect of metal-induced crystallization can only be achieved when the ratio of the thickness of the amorphous silicon film to the metal aluminum film is greater than 2:1. Therefore, the problem of metal contamination is the main problem. A technical bottleneck.
LIC技术指的是在激光的瞬间脉冲作用下，使薄膜在数十到数百纳秒内升至高温，薄膜表面产生热能效应实现了由非晶硅到多晶硅薄膜的转变。由于激光扫描的过程持续时间很短、激光光束的宽度很小，传递到衬底材料的热量很少，所以对衬底材料要求不是很严格。该技术存在的问题是所需的激光的能量非常大。另外，无论是MIC技术还是LIC技术，目前其晶化前驱物非晶硅薄膜一般都用PECVD方法获得，仍需要硅烷等危险气体。LIC technology refers to that under the action of instantaneous pulses of laser, the film is raised to a high temperature within tens to hundreds of nanoseconds, and the thermal effect generated on the surface of the film realizes the transformation from amorphous silicon to polysilicon film. Since the duration of the laser scanning process is very short, the width of the laser beam is small, and the heat transferred to the substrate material is very small, the requirements for the substrate material are not very strict. The problem with this technique is that the energy of the laser light required is very high. In addition, whether it is MIC technology or LIC technology, the crystallization precursor amorphous silicon thin film is generally obtained by PECVD method at present, and dangerous gases such as silane are still required.
如申请号为201310163296.4公开了一种低成本高效多晶硅基薄膜的制备方法，其工艺流程包括薄膜沉积和固相晶化两部分。首先，采用等离子增强型化学气相沉积法，在玻璃衬底上生长500-2000nm的前驱体硅基薄膜，通过调节反应气体中硅烷与氢气的比例，在薄膜内部引入不同含量的结晶成分；随后，将薄膜样品在500-600℃下退火处理4-12小时，薄膜内的非晶成分逐渐晶化，最终得到结晶性良好的多晶硅薄膜材料。该方法通过在前驱体硅基薄膜内引入结晶成分，固相晶化过程中不需要形核，有效降低了薄膜的晶化温度，缩短了晶化所需时间，但制备过程中仍需要危险气体硅烷。For example, the application number is 201310163296.4, which discloses a low-cost and high-efficiency polysilicon-based film preparation method, and its process includes two parts: film deposition and solid phase crystallization. First, a 500-2000nm precursor silicon-based film is grown on a glass substrate by plasma-enhanced chemical vapor deposition, and different contents of crystalline components are introduced into the film by adjusting the ratio of silane to hydrogen in the reaction gas; then, The film sample is annealed at 500-600° C. for 4-12 hours, the amorphous components in the film are gradually crystallized, and finally a polysilicon film material with good crystallinity is obtained. This method introduces crystalline components into the precursor silicon-based film, and does not require nucleation during solid-phase crystallization, which effectively reduces the crystallization temperature of the film and shortens the time required for crystallization, but dangerous gases are still required during the preparation process. silane.
有鉴于此，特提出本发明。In view of this, the present invention is proposed.
发明内容Contents of the invention
本发明的目的在于提供一种多晶硅薄膜材料的制备方法，该方法具有以下有益效果：(1)非晶硅薄膜和金属铝膜均采用磁控溅射技术获得，不需要硅烷等危险气体；(2)与常规的MIC技术相比，金属铝膜的厚度极薄，金属铝膜与非晶硅薄膜的厚度之比为1:16-60，比如：对于厚度为300nm的非晶硅薄膜，仅需5-19nm的金属铝膜即可，可大大降低金属污染；(3)与常规LIC技术相比，激光阈值能量大大降低，如对于360nm的非晶硅薄膜，22nm的金属铝膜辅助使得激光能量密度仅为3.46×104W/cm2就可以使硅薄膜晶化，晶相体积比已达到55％；而常规的LIC技术需要4.27×104W/cm2才能使薄膜开始晶化，且晶相体积比只有20％；(4)在磁控溅射技术依次沉积非晶硅薄膜和金属铝膜过程中，最高温度不超过150℃，是现有多晶硅薄膜制备工艺中温度最低的，因此可大大降低能耗。The object of the present invention is to provide a kind of preparation method of polysilicon film material, and this method has following beneficial effect: (1) amorphous silicon film and metallic aluminum film all adopt magnetron sputtering technology to obtain, do not need dangerous gases such as silane; 2) Compared with the conventional MIC technology, the thickness of the metal aluminum film is extremely thin, and the ratio of the thickness of the metal aluminum film to the amorphous silicon film is 1:16-60, for example: for an amorphous silicon film with a thickness of 300nm, only A metal aluminum film of 5-19nm is required, which can greatly reduce metal pollution; (3) Compared with conventional LIC technology, the laser threshold energy is greatly reduced. For example, for a 360nm amorphous silicon film, a 22nm metal aluminum film can assist the laser The silicon thin film can be crystallized with an energy density of only 3.46×104 W/cm2 , and the crystal phase volume ratio has reached 55%; while the conventional LIC technology requires 4.27×104 W/cm2 to start the crystallization of the thin film. And the crystal phase volume ratio is only 20%; (4) During the sequential deposition of amorphous silicon film and metal aluminum film by magnetron sputtering technology, the highest temperature does not exceed 150°C, which is the lowest temperature in the existing polysilicon film preparation process. Energy consumption can thus be significantly reduced.
为了实现本发明的上述目的，特采用以下技术方案：In order to realize the above-mentioned purpose of the present invention, special adopt following technical scheme:
一种多晶硅薄膜材料的制备方法，包括以下步骤：A preparation method of polysilicon thin film material, comprising the following steps:
在玻璃衬底上，采用磁控溅射技术依次沉积非晶硅薄膜和金属铝膜，得到复合薄膜；On the glass substrate, the amorphous silicon film and the metal aluminum film are sequentially deposited by magnetron sputtering technology to obtain a composite film;
对所述复合薄膜进行激光辐照，所述非晶硅薄膜晶化，即得所述多晶硅薄膜材料；irradiating the composite film with laser light to crystallize the amorphous silicon film to obtain the polysilicon film material;
其中，在磁控溅射技术依次沉积非晶硅薄膜和金属铝膜过程中，温度不高于150℃。Among them, during the sequential deposition of amorphous silicon film and metal aluminum film by magnetron sputtering technology, the temperature is not higher than 150°C.
本发明实施例提供的多晶硅薄膜材料的制备方法，非晶硅薄膜和金属铝膜均采用磁控溅射技术获得，不需要硅烷等危险气体；在磁控溅射技术依次沉积非晶硅薄膜和金属铝膜过程中，最高温度不超过150℃，采用廉价的玻璃衬底即可，多晶硅薄膜制备工艺中温度低，可大大降低能耗。In the preparation method of the polysilicon thin film material provided by the embodiment of the present invention, both the amorphous silicon thin film and the metal aluminum film are obtained by magnetron sputtering technology, and no dangerous gases such as silane are needed; the amorphous silicon thin film and the In the metal aluminum film process, the maximum temperature does not exceed 150°C, and a cheap glass substrate can be used. The low temperature in the polysilicon film preparation process can greatly reduce energy consumption.
优选地，所述非晶硅薄膜是以纯度为99.999％-99.9999％的本征硅靶利用磁控溅射技术沉积而得。该纯度的本征硅靶采用磁控溅射技术沉积方便易行，且温度低，沉积得到的非晶硅薄膜密度适当，利于晶化。Preferably, the amorphous silicon thin film is deposited from an intrinsic silicon target with a purity of 99.999%-99.9999% by magnetron sputtering technology. The intrinsic silicon target of this purity is deposited conveniently and easily by magnetron sputtering technology, and the temperature is low, and the density of the deposited amorphous silicon thin film is appropriate, which is beneficial to crystallization.
具体地，磁控溅射技术沉积非晶硅薄膜的具体条件为：Specifically, the specific conditions for depositing amorphous silicon thin films by magnetron sputtering technology are:
沉积气压为0.8-2.0Pa，辉光功率为60-80W，氩气流量为20-30sccm，衬底温度为100℃-150℃。The deposition pressure is 0.8-2.0Pa, the glow power is 60-80W, the argon flow rate is 20-30sccm, and the substrate temperature is 100°C-150°C.
实验结果表明随着辉光功率的增加，沉积气压的降低沉积速率增大，衬底温度对沉积速率的影响不大。在该磁控溅射技术沉积非晶硅薄膜的条件下，硅的沉积速率为10-13nm/min，实现了非晶硅薄膜的快速沉积，得到的非晶硅薄膜利于晶化。镀膜时间根据实际所需非晶硅薄膜的厚度调整。The experimental results show that with the increase of the glow power, the deposition rate increases with the decrease of the deposition pressure, but the substrate temperature has little effect on the deposition rate. Under the condition of depositing the amorphous silicon thin film by the magnetron sputtering technology, the deposition rate of silicon is 10-13nm/min, realizing rapid deposition of the amorphous silicon thin film, and the obtained amorphous silicon thin film is favorable for crystallization. The coating time is adjusted according to the actual required thickness of the amorphous silicon film.
优选地，所述金属铝膜是以纯度为99.999％-99.9999％的铝靶在所述非晶硅薄膜上利用磁控溅射技术沉积而成。该纯度的铝靶采用磁控溅射技术沉积方便易行，且温度低，沉积得到的金属铝膜密度适当，在激光辐照下利于非晶硅薄膜的晶化。Preferably, the metal aluminum film is deposited on the amorphous silicon film by using an aluminum target with a purity of 99.999%-99.9999% by magnetron sputtering technology. The aluminum target of this purity is deposited conveniently and easily by magnetron sputtering technology, and the temperature is low, and the density of the deposited metal aluminum film is appropriate, which is beneficial to the crystallization of the amorphous silicon film under laser irradiation.
具体地，磁控溅射技术沉积金属铝膜的具体条件为：Specifically, the specific conditions for depositing metal aluminum film by magnetron sputtering technology are:
沉积气压为1-2Pa，辉光功率为40-80W，氩气流量为20-30sccm，衬底温度为100-150℃。The deposition pressure is 1-2Pa, the glow power is 40-80W, the argon flow rate is 20-30sccm, and the substrate temperature is 100-150°C.
实验结果表明随着辉光功率的增加，沉积气压的降低沉积速率增大，衬底温度对沉积速率的影响不大。在该磁控溅射技术沉积金属铝膜的条件下，铝的沉积速率为9-12nm/min，实现了金属铝膜的快速沉积，并且得到的金属铝膜在激光辐照下利于非晶硅薄膜的晶化。镀膜时间根据实际所需金属铝膜的厚度调整。The experimental results show that with the increase of the glow power, the deposition rate increases with the decrease of the deposition pressure, but the substrate temperature has little effect on the deposition rate. Under the conditions of the deposition of metal aluminum film by magnetron sputtering technology, the deposition rate of aluminum is 9-12nm/min, which realizes the rapid deposition of metal aluminum film, and the obtained metal aluminum film is beneficial to amorphous silicon under laser irradiation. Crystallization of thin films. The coating time is adjusted according to the actual thickness of the metal aluminum film required.
经验证，金属铝膜与非晶硅薄膜的厚度之比为1:16-60可实现非晶硅薄膜的晶化，并且可大大降低金属污染。优选地，所述金属铝膜与所述非晶硅薄膜的厚度之比为1:16-60。如：金属铝膜与非晶硅薄膜的厚度之比可以选择为1:16、1:17、1:18、1:20、1:25、1:30、1:35、1:40、1:50、1:60等等。It has been verified that the ratio of the thickness of the metal aluminum film to the amorphous silicon film is 1:16-60, which can realize the crystallization of the amorphous silicon film and greatly reduce metal pollution. Preferably, the thickness ratio of the metal aluminum film to the amorphous silicon film is 1:16-60. For example: the ratio of the thickness of the metal aluminum film to the amorphous silicon film can be selected as 1:16, 1:17, 1:18, 1:20, 1:25, 1:30, 1:35, 1:40, 1 :50, 1:60, etc.
经验证，激光辐照采用的激光的波长为532nm，光斑直径为20-30μm，激光的能量密度为3.46×104W/cm2-9.61×104W/cm2可实现对非晶硅薄膜的晶化。优选地，所述激光辐照采用的激光的波长为532nm，光斑直径为20-30μm，激光的能量密度为3.46×104W/cm2-9.61×104W/cm2。It has been verified that the wavelength of the laser used for laser irradiation is 532nm, the diameter of the spot is 20-30μm, and the energy density of the laser is 3.46×104 W/cm2 -9.61×104 W/cm2 . of crystallization. Preferably, the wavelength of the laser used for the laser irradiation is 532nm, the spot diameter is 20-30μm, and the energy density of the laser is 3.46×104 W/cm2 -9.61×104 W/cm2 .
为了更好的对非晶硅薄膜进行晶化，优选地，所述激光对所述复合薄膜的扫描速率为0.8-1.5mm/s。In order to better crystallize the amorphous silicon film, preferably, the scanning rate of the laser on the composite film is 0.8-1.5 mm/s.
与现有技术相比，本发明的有益效果为：Compared with prior art, the beneficial effect of the present invention is:
(1)不需要硅烷等危险气体；(1) No need for dangerous gases such as silane;
(2)所需金属铝膜的厚度极薄，大大降低了金属污染；(2) The thickness of the required metal aluminum film is extremely thin, which greatly reduces metal pollution;
(3)硅薄膜晶化所需激光阈值能量大大降低，节约能源；(3) The laser threshold energy required for silicon thin film crystallization is greatly reduced, saving energy;
(4)工艺温度低，大大降低了能耗；(4) The process temperature is low, which greatly reduces energy consumption;
(5)得到的多晶硅薄膜材料晶相体积比高，晶界缺陷少；多晶硅薄膜材料的电学性能可控性高，重复性高。(5) The obtained polysilicon thin film material has a high crystal phase volume ratio and few grain boundary defects; the electrical properties of the polysilicon thin film material are highly controllable and repeatable.
附图说明Description of drawings
图1示出了本发明实施例中玻璃衬底-非晶硅薄膜-金属铝膜的纵剖面图；Fig. 1 shows the longitudinal sectional view of glass substrate-amorphous silicon thin film-metal aluminum film in the embodiment of the present invention;
图2示出了本发明实施例1制备的多晶硅薄膜材料的拉曼散射图；Fig. 2 shows the Raman scattering diagram of the polysilicon film material prepared in Example 1 of the present invention;
图3示出了本发明实施例1制备的多晶硅薄膜材料不同激光能量密度下的晶相体积比的曲线图；Fig. 3 shows the curve graph of the crystal phase volume ratio under different laser energy densities of the polysilicon thin film material prepared in Example 1 of the present invention;
图4示出了本发明实施例1中对照组中多晶硅薄膜材料的拉曼散射图；Fig. 4 shows the Raman scattering figure of the polysilicon film material in the control group in the embodiment of the present invention 1;
图5示出了本发明实施例1中对照组中多晶硅薄膜材料的不同激光能量密度下的晶相体积比的曲线图。Fig. 5 is a graph showing the crystal phase volume ratio of the polycrystalline silicon thin film material under different laser energy densities in the control group in Example 1 of the present invention.
附图标记：1、玻璃衬底；2、非晶硅薄膜；3、金属铝膜。Reference signs: 1. Glass substrate; 2. Amorphous silicon film; 3. Metal aluminum film.
具体实施方式Detailed ways
下面将结合实施例对本发明的实施方案进行详细描述，但是本领域技术人员将会理解，下列实施例仅用于说明本发明，而不应视为限制本发明的范围。实施例中未注明具体条件者，按照常规条件或制造商建议的条件进行。所用试剂或仪器未注明生产厂商者，均为可以通过市售获得的常规产品。Embodiments of the present invention will be described in detail below in conjunction with examples, but those skilled in the art will understand that the following examples are only for illustrating the present invention, and should not be considered as limiting the scope of the present invention. Those who do not indicate the specific conditions in the examples are carried out according to the conventional conditions or the conditions suggested by the manufacturer. The reagents or instruments used were not indicated by the manufacturer, and they were all commercially available conventional products.
实施例1Example 1
如图1所示，在玻璃衬底1上采用纯度为99.999％的本征硅靶利用磁控溅射技术沉积一层非晶硅薄膜2，具体工艺条件为：沉积气压为1Pa，辉光功率为80W，氩气流量为26sccm，衬底温度为150℃，沉积时间为30min，获得厚度为360nm的非晶硅薄膜2；As shown in Figure 1, a layer of amorphous silicon thin film 2 is deposited on a glass substrate 1 using an intrinsic silicon target with a purity of 99.999% by magnetron sputtering technology. The specific process conditions are: the deposition pressure is 1Pa, the glow power 80W, the argon gas flow rate is 26sccm, the substrate temperature is 150°C, and the deposition time is 30min, to obtain an amorphous silicon thin film 2 with a thickness of 360nm;
非晶硅薄膜2沉积完成之后，在同一真空腔体内利用纯度为99.999％的铝靶在非晶硅薄膜2上溅射沉积一层金属铝膜3，其工艺条件如下：沉积气压为1Pa，辉光功率为60W，氩气流量为26sccm，衬底温度为100℃，镀膜时间为2min，得到厚度为22nm的金属铝膜3；After the deposition of the amorphous silicon film 2 is completed, a metal aluminum film 3 is sputtered and deposited on the amorphous silicon film 2 in the same vacuum chamber using an aluminum target with a purity of 99.999%. The process conditions are as follows: the deposition pressure is 1 Pa, The optical power is 60W, the flow rate of argon gas is 26sccm, the substrate temperature is 100°C, and the coating time is 2min, and a metal aluminum film 3 with a thickness of 22nm is obtained;
将制备好的玻璃衬底-非晶硅薄膜-金属铝膜样品放置在2D位移台上，2D位移台可沿x轴和y轴方向自动移动，对样品进行激光辐照，激光光束照在样品上，激光光束由波长为532nm的连续固体激光器发出，照在样品上的激光光斑的直径为20μm，能量密度为3.46×104W/cm2-9.61×104W/cm2，激光对样品的扫描速率为1.2mm/s，激光扫描完整个样品，激光辐照完成；Place the prepared glass substrate-amorphous silicon film-metal aluminum film sample on the 2D translation stage, the 2D translation stage can automatically move along the x-axis and y-axis direction, and irradiate the sample with laser beam, and the laser beam shines on the sample Above, the laser beam is emitted by a continuous solid-state laser with a wavelength of 532nm. The diameter of the laser spot irradiated on the sample is 20μm, and the energy density is 3.46×104 W/cm2 -9.61×104 W/cm2 . The scanning rate is 1.2mm/s, the laser scans the entire sample, and the laser irradiation is completed;
对得到的多晶硅薄膜材料进行拉曼散射测试，结果如图2所示，从图2可以看出，在激光能能量密度为3.46×104W/cm2-9.61×104W/cm2范围内，样品均已晶化，且随着激光能量密度的增加，样品的晶化峰逐渐增强。Raman scattering test was carried out on the obtained polysilicon thin film material, and the results are shown in Figure 2. From Figure 2, it can be seen that when the laser energy energy density is in the range of 3.46×104 W/cm2 -9.61×104 W/cm2 In , the samples have been crystallized, and with the increase of laser energy density, the crystallization peak of the samples is gradually enhanced.
对拉曼光谱进行高斯拟合，估算样品不同激光能量密度下的晶相体积比f，结果如图3所示。从图3可以看出，随着激光能量密度的增加，晶相体积比逐渐增大。当激光能量密度达到9.61×104W/cm2时，多晶硅薄膜的晶相体积比达到了86％。Gaussian fitting was performed on the Raman spectrum to estimate the crystal phase volume ratio f of the sample under different laser energy densities, and the results are shown in Figure 3. It can be seen from Figure 3 that with the increase of laser energy density, the crystal phase volume ratio gradually increases. When the laser energy density reaches 9.61×104 W/cm2 , the crystal phase volume ratio of the polysilicon film reaches 86%.
同时，设置了对照试验，对照试验没有22nm的铝膜，其他条件不变，即相当于常规的激光晶化工艺，对照试验得到的多晶硅薄膜材料进行拉曼散射测试，结果如图4所示。从图4可以看出，在激光能能量密度为3.46×104W/cm2时，非晶硅薄膜并没有晶化，只有当激光能量密度增加到4.27×104W/cm2时，样品才有微量的晶化。At the same time, a control experiment was set up. The control experiment did not have a 22nm aluminum film, and other conditions remained unchanged, that is, it was equivalent to a conventional laser crystallization process. The polysilicon thin film material obtained in the control experiment was tested by Raman scattering, and the results are shown in Figure 4. It can be seen from Figure 4 that when the laser energy density is 3.46×104 W/cm2 , the amorphous silicon film is not crystallized, only when the laser energy density increases to 4.27×104 W/cm2 , the sample There is only a small amount of crystallization.
对对照组的拉曼光谱进行高斯拟合，估算样品不同激光能量密度下的晶相体积比f，结果如图5所示。从图5可以看出，激光能量密度达到9.61×104W/cm2时，多晶硅薄膜的晶相体积比只有57.6％。Gaussian fitting was performed on the Raman spectrum of the control group to estimate the crystal phase volume ratio f of the sample under different laser energy densities, and the results are shown in Figure 5. It can be seen from Figure 5 that when the laser energy density reaches 9.61×104 W/cm2 , the crystal phase volume ratio of the polysilicon film is only 57.6%.
实施例2Example 2
如图1所示，在玻璃衬底1上采用纯度为99.9999％的本征硅靶利用磁控溅射技术沉积一层非晶硅薄膜2，具体工艺条件为：沉积气压为0.8Pa，辉光功率为80W，氩气流量为20sccm，衬底温度为150℃，沉积时间为25min，获得厚度为325nm的非晶硅薄膜2；As shown in Figure 1, a layer of amorphous silicon thin film 2 is deposited on a glass substrate 1 using an intrinsic silicon target with a purity of 99.9999% by magnetron sputtering technology. The specific process conditions are: the deposition pressure is 0.8Pa, the glow The power is 80W, the flow rate of argon gas is 20sccm, the substrate temperature is 150°C, and the deposition time is 25min to obtain an amorphous silicon thin film 2 with a thickness of 325nm;
非晶硅薄膜2沉积完成之后，在同一真空腔体内利用纯度为99.9999％的铝靶在非晶硅薄膜2上溅射沉积一层金属铝膜3，其工艺条件如下：沉积气压为1Pa，辉光功率为80W，氩气流量为20sccm，衬底温度为150℃，镀膜时间为1.5min，得到厚度为18nm的金属铝膜3；After the deposition of the amorphous silicon film 2 is completed, a metal aluminum film 3 is deposited on the amorphous silicon film 2 by sputtering with an aluminum target with a purity of 99.9999% in the same vacuum chamber. The process conditions are as follows: the deposition pressure is 1 Pa, The optical power is 80W, the flow rate of argon gas is 20sccm, the substrate temperature is 150°C, and the coating time is 1.5min, to obtain a metal aluminum film 3 with a thickness of 18nm;
将制备好的玻璃衬底-非晶硅薄膜-金属铝膜样品放置在2D位移台上，2D位移台可沿x轴和y轴方向自动移动，对样品进行激光辐照，激光光束照在样品上，激光光束由波长为532nm的连续固体激光器发出，照在样品上的激光光斑的直径为30μm，能量密度为3.46×104W/cm2-9.61×104W/cm2，激光对样品的扫描速率为1.5mm/s，激光扫描完整个样品，激光辐照完成；Place the prepared glass substrate-amorphous silicon film-metal aluminum film sample on the 2D translation stage, the 2D translation stage can automatically move along the x-axis and y-axis direction, and irradiate the sample with laser beam, and the laser beam shines on the sample Above, the laser beam is emitted by a continuous solid-state laser with a wavelength of 532nm. The diameter of the laser spot irradiated on the sample is 30μm, and the energy density is 3.46×104 W/cm2 -9.61×104 W/cm2 . The scanning rate is 1.5mm/s, the laser scans the entire sample, and the laser irradiation is completed;
对得到的多晶硅薄膜材料进行拉曼散射测试，结果与图2基本一致；对拉曼光谱进行高斯拟合，估算样品不同激光能量密度下的晶相体积比f，结果与图3基本一致。Raman scattering test was carried out on the obtained polysilicon thin film material, and the results were basically consistent with those in Figure 2; Gaussian fitting was performed on the Raman spectrum to estimate the crystal phase volume ratio f of the sample under different laser energy densities, and the results were basically consistent with Figure 3.
同时，设置了对照试验，对照试验没有18nm的铝膜，其他条件不变，即相当于常规的激光晶化工艺，对照试验得到的多晶硅薄膜材料进行拉曼散射测试，结果与图4基本一致，在激光能能量密度为3.46×104W/cm2时，非晶硅薄膜并没有晶化，只有当激光能量密度增加到4.27×104W/cm2时，样品才有微量的晶化。At the same time, a control experiment was set up. The control experiment did not have an aluminum film of 18nm, and other conditions remained unchanged, that is, it was equivalent to a conventional laser crystallization process. The polysilicon thin film material obtained in the control experiment was tested by Raman scattering, and the results were basically consistent with those shown in Figure 4. When the laser energy density is 3.46×104 W/cm2 , the amorphous silicon thin film is not crystallized, only when the laser energy density increases to 4.27×104 W/cm2 , the sample has a slight amount of crystallization.
对对照组的拉曼光谱进行高斯拟合，估算样品不同激光能量密度下的晶相体积比f，结果与图5基本一致。激光能量密度达到9.61×104W/cm2时，多晶硅薄膜的晶相体积比只有57.8％。Gaussian fitting was performed on the Raman spectrum of the control group to estimate the crystal phase volume ratio f of the sample under different laser energy densities, and the results were basically consistent with those shown in Figure 5. When the laser energy density reaches 9.61×104 W/cm2 , the crystal phase volume ratio of the polysilicon film is only 57.8%.
实施例3Example 3
如图1所示，在玻璃衬底1上采用纯度为99.9999％的本征硅靶利用磁控溅射技术沉积一层非晶硅薄膜2，具体工艺条件为：沉积气压为2.0Pa，辉光功率为60W，氩气流量为30sccm，衬底温度为100℃，沉积时间为36min，获得厚度为360nm的非晶硅薄膜2；As shown in Figure 1, a layer of amorphous silicon film 2 is deposited on a glass substrate 1 by using an intrinsic silicon target with a purity of 99.9999% by magnetron sputtering technology. The specific process conditions are: the deposition pressure is 2.0Pa, the glow The power is 60W, the flow rate of argon gas is 30sccm, the substrate temperature is 100°C, and the deposition time is 36min to obtain an amorphous silicon thin film 2 with a thickness of 360nm;
非晶硅薄膜2沉积完成之后，在同一真空腔体内利用纯度为99.9999％的铝靶在非晶硅薄膜2上溅射沉积一层金属铝膜3，其工艺条件如下：沉积气压为2Pa，辉光功率为40W，氩气流量为30sccm，衬底温度为100℃，镀膜时间为40s，得到厚度为6nm的金属铝膜3；After the deposition of the amorphous silicon film 2 is completed, a metal aluminum film 3 is sputtered and deposited on the amorphous silicon film 2 in the same vacuum chamber using an aluminum target with a purity of 99.9999%. The process conditions are as follows: the deposition pressure is 2Pa, The optical power is 40W, the flow rate of argon gas is 30sccm, the substrate temperature is 100°C, and the coating time is 40s to obtain a metal aluminum film 3 with a thickness of 6nm;
将制备好的玻璃衬底-非晶硅薄膜-金属铝膜样品放置在2D位移台上，2D位移台可沿x轴和y轴方向自动移动，对样品进行激光辐照，激光光束照在样品上，激光光束由波长为532nm的连续固体激光器发出，照在样品上的激光光斑的直径为25μm，能量密度为3.46×104W/cm2-9.61×104W/cm2，激光对样品的扫描速率为0.8mm/s，激光扫描完整个样品，激光辐照完成；Place the prepared glass substrate-amorphous silicon film-metal aluminum film sample on the 2D translation stage, the 2D translation stage can automatically move along the x-axis and y-axis direction, and irradiate the sample with laser beam, and the laser beam shines on the sample Above, the laser beam is emitted by a continuous solid-state laser with a wavelength of 532nm. The diameter of the laser spot irradiated on the sample is 25μm, and the energy density is 3.46×104 W/cm2 -9.61×104 W/cm2 . The scan rate is 0.8mm/s, the laser scans the entire sample, and the laser irradiation is completed;
对得到的多晶硅薄膜材料进行拉曼散射测试，结果与图2基本一致，并对拉曼光谱进行高斯拟合，估算样品不同激光能量密度下的晶相体积比f，结果表明，在激光能量密度为3.46×104W/cm2时，薄膜已开始晶化，晶相体积比为21.1％，且随激光能量密度的增加，薄膜晶相体积比逐渐增大，与图3趋势基本一致。当激光能量密度达到9.61×104W/cm2时，薄膜晶相体积比达到72.1％。同时，设置了对照试验，对照试验没有6nm的铝膜，其他条件不变，即相当于常规的激光晶化工艺，对照试验得到的多晶硅薄膜材料进行拉曼散射测试，结果与图4基本一致，在激光能能量密度为3.46×104W/cm2时，非晶硅薄膜并没有晶化，只有当激光能量密度增加到4.27×104W/cm2时，样品才有微量的晶化。Raman scattering test was carried out on the obtained polysilicon thin film material, and the results were basically consistent with those shown in Figure 2. Gaussian fitting was performed on the Raman spectrum to estimate the crystal phase volume ratio f of the sample under different laser energy densities. The results showed that at laser energy densities When the value is 3.46×104 W/cm2 , the film has begun to crystallize, and the crystal phase volume ratio is 21.1%. With the increase of laser energy density, the crystal phase volume ratio of the film gradually increases, which is basically consistent with the trend in Figure 3. When the laser energy density reaches 9.61×104 W/cm2 , the crystal phase volume ratio of the thin film reaches 72.1%. At the same time, a control experiment was set up. The control experiment did not have a 6nm aluminum film, and other conditions remained unchanged, that is, it was equivalent to a conventional laser crystallization process. The polysilicon thin film material obtained in the control experiment was tested by Raman scattering, and the results were basically consistent with those shown in Figure 4. When the laser energy density is 3.46×104 W/cm2 , the amorphous silicon thin film is not crystallized, only when the laser energy density increases to 4.27×104 W/cm2 , the sample has a slight amount of crystallization.
对对照组的拉曼光谱进行高斯拟合，估算样品不同激光能量密度下的晶相体积比f，结果与图5基本一致。激光能量密度达到9.61×104W/cm2时，多晶硅薄膜的晶相体积比只有57.6％。Gaussian fitting was performed on the Raman spectrum of the control group to estimate the crystal phase volume ratio f of the sample under different laser energy densities, and the results were basically consistent with those shown in Figure 5. When the laser energy density reaches 9.61×104 W/cm2 , the crystal phase volume ratio of the polysilicon film is only 57.6%.
实施例4Example 4
如图1所示，在玻璃衬底1上采用纯度为99.999％的本征硅靶利用磁控溅射技术沉积一层非晶硅薄膜2，具体工艺条件为：沉积气压为1.3Pa，辉光功率为70W，氩气流量为24sccm，衬底温度为140℃，沉积时间为30min，获得厚度为330nm的非晶硅薄膜2；As shown in Figure 1, a layer of amorphous silicon thin film 2 is deposited on a glass substrate 1 using an intrinsic silicon target with a purity of 99.999% using magnetron sputtering technology. The specific process conditions are: the deposition pressure is 1.3Pa, the glow The power is 70W, the flow rate of argon gas is 24sccm, the substrate temperature is 140°C, and the deposition time is 30min, to obtain an amorphous silicon thin film 2 with a thickness of 330nm;
非晶硅薄膜2沉积完成之后，在同一真空腔体内利用纯度为99.9999％的铝靶在非晶硅薄膜2上溅射沉积一层金属铝膜3，其工艺条件如下：沉积气压为1.5Pa，辉光功率为60W，氩气流量为25sccm，衬底温度为125℃，镀膜时间为1min，得到厚度为10nm的金属铝膜3；After the deposition of the amorphous silicon film 2 is completed, a metal aluminum film 3 is deposited on the amorphous silicon film 2 by sputtering with an aluminum target with a purity of 99.9999% in the same vacuum chamber. The process conditions are as follows: the deposition pressure is 1.5Pa, The glow power is 60W, the argon gas flow rate is 25sccm, the substrate temperature is 125°C, and the coating time is 1min, to obtain a metal aluminum film 3 with a thickness of 10nm;
将制备好的玻璃衬底-非晶硅薄膜-金属铝膜样品放置在2D位移台上，2D位移台可沿x轴和y轴方向自动移动，对样品进行激光辐照，激光光束照在样品上，激光光束由波长为532nm的连续固体激光器发出，照在样品上的激光光斑的直径为25μm，能量密度为3.46×104W/cm2-9.61×104W/cm2，激光对样品的扫描速率为1.2mm/s，激光扫描完整个样品，激光辐照完成；Place the prepared glass substrate-amorphous silicon film-metal aluminum film sample on the 2D translation stage, the 2D translation stage can automatically move along the x-axis and y-axis direction, and irradiate the sample with laser beam, and the laser beam shines on the sample Above, the laser beam is emitted by a continuous solid-state laser with a wavelength of 532nm. The diameter of the laser spot irradiated on the sample is 25μm, and the energy density is 3.46×104 W/cm2 -9.61×104 W/cm2 . The scanning rate is 1.2mm/s, the laser scans the entire sample, and the laser irradiation is completed;
对得到的多晶硅薄膜材料进行拉曼散射测试，结果与图2基本一致；并对拉曼光谱进行高斯拟合。结果表明，在激光能量密度为3.46×104W/cm2时，薄膜已开始晶化，晶相体积比为35.2％，且随激光能量密度的增加，薄膜晶相体积比逐渐增大，与图3趋势基本一致。当激光能量密度达到9.61×104W/cm2时，薄膜晶相体积比达到78.3％。同时，设置了对照试验，对照试验没有10nm的铝膜，其他条件不变，即相当于常规的激光晶化工艺，对照试验得到的多晶硅薄膜材料进行拉曼散射测试，结果与图4基本一致，在激光能能量密度为3.46×104W/cm2时，非晶硅薄膜并没有晶化，只有当激光能量密度增加到4.27×104W/cm2时，样品才有微量的晶化。The Raman scattering test was carried out on the obtained polysilicon thin film material, and the result was basically consistent with that in Figure 2; Gaussian fitting was performed on the Raman spectrum. The results show that when the laser energy density is 3.46×104 W/cm2 , the film has begun to crystallize, and the crystal phase volume ratio is 35.2%. The trend in Figure 3 is basically the same. When the laser energy density reaches 9.61×104 W/cm2 , the crystal phase volume ratio of the thin film reaches 78.3%. At the same time, a control experiment was set up. The control experiment did not have a 10nm aluminum film, and other conditions remained unchanged, that is, it was equivalent to a conventional laser crystallization process. The polysilicon thin film material obtained in the control experiment was tested by Raman scattering, and the results were basically consistent with those shown in Figure 4. When the laser energy density is 3.46×104 W/cm2 , the amorphous silicon thin film is not crystallized, only when the laser energy density increases to 4.27×104 W/cm2 , the sample has a small amount of crystallization.
对对照组的拉曼光谱进行高斯拟合，估算样品不同激光能量密度下的晶相体积比f，结果与图5基本一致。激光能量密度达到9.61×104W/cm2时，多晶硅薄膜的晶相体积比只有57.8％。Gaussian fitting was performed on the Raman spectrum of the control group to estimate the crystal phase volume ratio f of the sample under different laser energy densities, and the results were basically consistent with those shown in Figure 5. When the laser energy density reaches 9.61×104W/cm2, the crystal phase volume ratio of the polysilicon film is only 57.8%.
将实施例1-4获得的多晶硅薄膜材料进行扫描电镜测试，从扫描电镜照片可以看到本发明实施例制得的多晶硅薄膜材料质地均匀，晶界缺陷极少；将实施例1-4获得的多晶硅薄膜材料测试电学性能，得到该材料的载流子迁移率高，同时可控性好，重复性高。The polysilicon thin film material that embodiment 1-4 obtains is carried out scanning electron microscope test, can see that the polysilicon thin film material quality that the embodiment of the present invention makes is uniform from the scanning electron microscope photo, grain boundary defect is few; The embodiment 1-4 obtains The electrical properties of the polysilicon thin film material are tested, and it is obtained that the material has high carrier mobility, good controllability and high repeatability.
综上可以得出，本发明提供的多晶硅薄膜材料的制备方法不需要硅烷等危险气体；所需金属铝膜的厚度极薄，大大降低了金属污染；硅薄膜晶化所需激光阈值能量大大降低，节约能源；磁控溅射技术温度低，大大降低了能耗；得到的多晶硅薄膜材料晶相体积比高，晶界缺陷少；多晶硅薄膜材料的载流子迁移率高，电学性能可控性好，重复性高。In summary, it can be concluded that the preparation method of the polycrystalline silicon thin film material provided by the present invention does not require dangerous gases such as silane; the thickness of the required metal aluminum film is extremely thin, which greatly reduces metal pollution; the laser threshold energy required for silicon thin film crystallization is greatly reduced , saving energy; the temperature of magnetron sputtering technology is low, which greatly reduces energy consumption; the obtained polysilicon thin film material has a high crystal phase volume ratio and less grain boundary defects; the polysilicon thin film material has high carrier mobility and controllable electrical properties Well, high repeatability.
尽管已用具体实施例来说明和描述了本发明，然而应意识到，在不背离本发明的精神和范围的情况下可以作出许多其它的更改和修改。因此，这意味着在所附权利要求中包括属于本发明范围内的所有这些变化和修改。While particular embodiments of the invention have been illustrated and described, it should be appreciated that various other changes and modifications can be made without departing from the spirit and scope of the invention. It is therefore intended to cover in the appended claims all such changes and modifications that are within the scope of this invention.
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| CN201410555667.8ACN104392908A (en) | 2014-10-17 | 2014-10-17 | Preparation method of polysilicon thin film material |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104790032A (en)* | 2015-03-16 | 2015-07-22 | 大连大学 | Method for laser pulse sputtering deposition preparation of polycrystalline silicon thin film |
| CN105506734A (en)* | 2015-12-18 | 2016-04-20 | 浙江师范大学 | Polycrystalline silicon film and low-temperature preparation method thereof |
| WO2024230133A1 (en)* | 2023-05-08 | 2024-11-14 | 南京邮电大学 | Method for preparing monocrystalline silicon film based on laser interference technology |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040266189A1 (en)* | 1998-07-10 | 2004-12-30 | Lg Lcd Inc. | Method of crystallizing amorphous silicon layer and crystallizing apparatus thereof |
| CN101019214A (en)* | 2004-08-05 | 2007-08-15 | 加州理工大学 | Method for fabricating crystalline silicon |
| CN101908471A (en)* | 2010-04-07 | 2010-12-08 | 江苏华创光电科技有限公司 | Method for preparing large-area polycrystalline film |
| CN103060768A (en)* | 2013-01-17 | 2013-04-24 | 云南师范大学 | Low-temperature rapid crystallization method for amorphous silicon film |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20040266189A1 (en)* | 1998-07-10 | 2004-12-30 | Lg Lcd Inc. | Method of crystallizing amorphous silicon layer and crystallizing apparatus thereof |
| CN101019214A (en)* | 2004-08-05 | 2007-08-15 | 加州理工大学 | Method for fabricating crystalline silicon |
| CN101908471A (en)* | 2010-04-07 | 2010-12-08 | 江苏华创光电科技有限公司 | Method for preparing large-area polycrystalline film |
| CN103060768A (en)* | 2013-01-17 | 2013-04-24 | 云南师范大学 | Low-temperature rapid crystallization method for amorphous silicon film |
| Title |
|---|
| 唐正霞: "100微米大晶粒薄膜铝诱导法的制备", 《功能材料》* |
| 王成龙，范多旺: "不同形貌衬底铝诱导ploy-Si薄膜的制备及表征", 《光谱学与光谱分析》* |
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104790032A (en)* | 2015-03-16 | 2015-07-22 | 大连大学 | Method for laser pulse sputtering deposition preparation of polycrystalline silicon thin film |
| CN105506734A (en)* | 2015-12-18 | 2016-04-20 | 浙江师范大学 | Polycrystalline silicon film and low-temperature preparation method thereof |
| WO2024230133A1 (en)* | 2023-05-08 | 2024-11-14 | 南京邮电大学 | Method for preparing monocrystalline silicon film based on laser interference technology |
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| RJ01 | Rejection of invention patent application after publication | Application publication date:20150304 |