CN112903733B - A kind of super-resolution analysis method of transmission electron microscope energy spectrum - Google Patents
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Abstract
Description
技术领域technical field
本发明属于矿产资源勘查与微量元素化学检测领域，尤其涉及一种透射电镜能谱超分辨分析方法。The invention belongs to the field of mineral resource exploration and chemical detection of trace elements, in particular to a transmission electron microscope energy spectrum super-resolution analysis method.
背景技术Background technique
关键金属具有“稀”、“伴”、“细”的特点，通常以极小矿物、类质同象、吸附离子等形态赋存在矿石矿物中。厘清关键金属元素在矿石矿物中的赋存状态不仅可以为矿床因研究提供重要数据，而且是提高关键技术元素高效清洁利用水平的重要基础。Key metals have the characteristics of "rareness", "partner" and "fineness", and usually occur in ore minerals in the form of extremely small minerals, isomorphism, and adsorbed ions. Clarifying the occurrence state of key metal elements in ore minerals can not only provide important data for ore deposit research, but also an important basis for improving the efficient and clean utilization of key technical elements.
现今，在微米及亚微米尺度，微量元素在矿物岩石中的赋存状态鉴定多以电子探针、LA-ICP-MS、二次离子质谱等微区分析设备进行分析，而那里尺度多应用透射电子显微分析平台。透射电子显微镜功能强大，在纳米地球科学研究领域起到了至关重要的作用，其中透射电镜的元素分析模块多为能谱仪，而能谱仪的分辨率(125ev)较低，容易重叠，导致主量元素的谱峰对微量元素的谱峰产生很强的干扰。此外，能谱仪的检出限(理论检出限0.1-0.5％)也在微量元素分析中难以达到要求。矿物中的微量元素，如战略性元素稀土元素在矿物中的含量为几百ppm(10-6)。例如，中国的离子吸附性稀土矿床，供应了世界上90％以上的重稀土元素，而该类矿床稀土元素多赋存于微粒矿物(小于2um)上，但进一步在纳米尺度的研究，就因为透射电镜能谱的元素实际检出限难以达到要求，而面临阻碍；磷块岩型稀土矿床，稀土元素赋存于纳米磷灰石之中，但是，由于在纳米尺度研究中，常规使用能谱检出稀土元素检测不出，这导致该矿床的稀土元素赋存研究难以进行下去。Nowadays, at the micron and submicron scales, the identification of the occurrence state of trace elements in minerals and rocks is mostly analyzed by micro-analysis equipment such as electron probes, LA-ICP-MS, and secondary ion mass spectrometry. Electron Microanalysis Platform. The transmission electron microscope is powerful and plays a vital role in the field of nano-geoscience research. Most of the elemental analysis modules of the transmission electron microscope are energy spectrometers, and the resolution of the energy spectrometer (125ev) is low and easy to overlap, resulting The spectral peaks of major elements have strong interference with the spectral peaks of trace elements. In addition, the detection limit of energy spectrometer (theoretical detection limit 0.1-0.5%) is also difficult to meet the requirements in trace element analysis. The content of trace elements in minerals, such as strategic elements rare earth elements, is several hundred ppm (10 -6 ). For example, China's ion-adsorbing rare earth deposits supply more than 90% of the world's heavy rare earth elements, and rare earth elements in such deposits are mostly found in particulate minerals (less than 2um). The actual detection limit of elements in TEM energy spectrum is difficult to meet the requirements, and it is faced with obstacles; in phosphorite-type rare earth deposits, rare earth elements are present in nano-apatite. However, due to the routine use of energy spectrum in nano-scale research The rare earth elements cannot be detected, which makes it difficult to carry out the research on the occurrence of rare earth elements in this deposit.
发明内容SUMMARY OF THE INVENTION
本发明的目的在于解决上述现有技术存在的缺陷，提供一种透射电镜能谱超分辨分析方法。The purpose of the present invention is to solve the above-mentioned defects of the prior art, and to provide a super-resolution analysis method of transmission electron microscope energy spectrum.
本发明采用如下技术方案：The present invention adopts following technical scheme:
本发明提供一种透射电镜能谱超分辨分析方法，所述方法包括以下步骤：The invention provides a transmission electron microscope energy spectrum super-resolution analysis method, which comprises the following steps:
步骤1.目标样品的选择与分析；Step 1. Selection and analysis of target samples;
步骤2.微量元素组成分析样品的准备；Step 2. Preparation of samples for trace element composition analysis;
步骤3.目标样品的性质与元素组成分析(是否为电子束敏感样品、样品的主量元素和目标微量元素组成)；Step 3. Analysis of the properties and elemental composition of the target sample (whether it is an electron beam sensitive sample, the composition of the major elements of the sample and the target trace elements);
步骤4.根据需要制备透射电子显微镜观察样品；Step 4. Prepare transmission electron microscope observation samples as needed;
步骤5.对上一步制备样品，放入透射电子显微镜进行形貌观察，寻找合适的分析位置；
步骤6.查询相关元素的X射线光电子能谱仪的峰位，重点区别出可能与目标微量元素峰位有干扰的主量元素，并找寻能够与主量元素能谱峰位区别开的微量元素的关键峰位；Step 6. Query the peak positions of the X-ray photoelectron spectrometer of related elements, focus on identifying the major elements that may interfere with the peak positions of the target trace elements, and search for trace elements that can be distinguished from the peak positions of the major elements. The key peak position of ;
步骤7.针对微量元素检测需求，不采用传统的STEM模式进行能谱分析，而采用TEM模式在平行光模式下进行能谱信号采集，极大的提高能谱信号采集量，从而达到在纳米尺度下进行微量元素分析的目的。Step 7. For the detection requirements of trace elements, instead of using the traditional STEM mode for energy spectrum analysis, the TEM mode is used to collect the energy spectrum signal in the parallel light mode, which greatly improves the amount of energy spectrum signal collection, so as to achieve the nanometer scale. for the purpose of trace element analysis.
所述步骤(1)具体包括如下步骤：通过肉眼和显微镜鉴定矿物岩石基本分类；根据矿物岩石类型借助相应化学分析方法确定目标样品的微量元素种类与含量；在完成化学分析后，选择含有达到成矿品位的微量元素的矿物岩石作为目标样品。The step (1) specifically includes the following steps: identifying the basic classification of minerals and rocks by the naked eye and a microscope; determining the types and contents of trace elements of the target sample by means of corresponding chemical analysis methods according to the types of minerals and rocks; Mineral-grade mineral rocks with trace elements were used as target samples.
所述步骤(3)中矿物物相鉴定，形貌观察、元素组成分析方法包括但不限于如下可用于样品表面形貌分析的显微设备；微区X射线衍射方法(微区束斑通常小于100微米)、粉末X射线衍射方法、光学显微镜、扫描电子显微镜、原子力显微镜、ICP-OES、ICP-MS、电子探针、电子能谱、激光剥蚀-电感耦合等离子质谱、二次离子质谱方法。In the step (3), mineral phase identification, morphology observation, and elemental composition analysis methods include but are not limited to the following microscopic equipment that can be used for sample surface morphology analysis; 100 microns), powder X-ray diffraction method, optical microscope, scanning electron microscope, atomic force microscope, ICP-OES, ICP-MS, electron probe, electron spectroscopy, laser ablation-inductively coupled plasma mass spectrometry, secondary ion mass spectrometry methods.
用光学显微镜完成岩石薄片微米尺度下对矿物进行形貌观察，以及宏观矿物分布特点；Use optical microscope to observe the morphology of minerals at the micron scale of rock thin slices, as well as the distribution characteristics of macroscopic minerals;
用扫描电子显微镜完成在微米尺度下研究矿物形貌，分布关系及元素组成；Using scanning electron microscope to complete the study of mineral morphology, distribution relationship and element composition at the micron scale;
用激光剥蚀-电感耦合的离子质谱LA-ICP-MS完成在微米尺度下，用于原位检测矿物的微量元素含量；Laser ablation-inductively coupled ion mass spectrometry LA-ICP-MS was used to detect the trace element content of minerals in situ at the micron scale;
用二次离子质谱SIMS完成在微米尺度下，用于原位检测矿物的微量元素含量。所述步骤(7)中分析方法主要为：①在透射电镜TEM平行光模式下，对目标区域进行长时间特征X射线信号采集，能够极大的提高能谱信号的计数，从而实现对目标微量元素的分析；Completed with secondary ion mass spectrometry SIMS at the micron scale, for in situ detection of trace element content in minerals. The analysis method in the step (7) is mainly as follows: 1. In the TEM parallel light mode of the transmission electron microscope, long-time characteristic X-ray signal acquisition is performed on the target area, which can greatly improve the count of the energy spectrum signal, so as to realize the detection of the target trace amount. elemental analysis;
②针对样品的元素组成，根据主量元素与微量元素峰位进行分析，寻找与主量元素峰位不产生重叠的微量元素的峰位；②According to the element composition of the sample, analyze according to the peak positions of major elements and trace elements, and find the peak positions of trace elements that do not overlap with the peak positions of major elements;
③根据特殊形状的分析区域，可以通过调整透射电镜的C2镜来改变光斑的形状来进行能谱信号采集；③According to the analysis area of special shape, the energy spectrum signal can be collected by adjusting the C2 mirror of the transmission electron microscope to change the shape of the spot;
④针对电子束敏感样品，可适当减少电流强度，扩大光斑直径，来进行能谱信号采集。④ For electron beam sensitive samples, the current intensity can be appropriately reduced and the spot diameter can be enlarged to collect energy spectrum signals.
本发明的有益效果：Beneficial effects of the present invention:
本发明能够在纳米尺度下，对样品微量元素进行检测，极大的提高了透射电镜能谱分析的实际应用检出限，也提出了样品中微量元素被主量元素信号干扰的解决办法，并且，本发明也可以应用于电子束敏感样品的能谱分析。发明步骤中可根据实际情况需要按照从前至后的顺序，跳过某些步骤进行任意组合。The invention can detect the trace elements of the sample at the nanometer scale, greatly improves the detection limit of the actual application of the transmission electron microscope energy spectrum analysis, and also proposes a solution for the trace elements in the sample to be interfered by the signal of the major element, and , the present invention can also be applied to the energy spectrum analysis of electron beam sensitive samples. In the invention steps, according to the actual situation, some steps can be skipped and combined arbitrarily according to the order from the front to the back.
(1)本发明提供了一种透射电镜能谱超分辨分析方法，能够极大的提高透射电镜能谱的元素检测效率，能够在纳米科学的研究中对微量元素分析提供帮助。(1) The present invention provides a transmission electron microscope energy spectrum super-resolution analysis method, which can greatly improve the element detection efficiency of the transmission electron microscope energy spectrum, and can provide help for the analysis of trace elements in the research of nanoscience.
(2)本发明对于关键金属元素的赋存状态研究中因元素含量低，主量元素干扰、电子束敏感样品元素含量分析等问题提供了解决办法，为提升诸多难选难提取的关键金属矿产资源的开发利用水平提供基础保障。(2) The present invention provides a solution to the problems of low element content, interference of major elements, element content analysis of electron beam-sensitive samples, etc. in the research on the occurrence state of key metal elements, and improves many difficult-to-select and difficult-to-extract key metal minerals. The level of resource development and utilization provides a basic guarantee.
(3)本发明对于透射电镜研究地学样品中的化学元素分析具有优势，因为，地学样品大多为电子束敏感样品，而本方法能够最大程度的对样品进行保护，减少电子束对样品的损伤。(3) The present invention has advantages for the analysis of chemical elements in TEM samples, because most of the geological samples are electron beam sensitive samples, and this method can protect the samples to the greatest extent and reduce the damage to the samples by electron beams.
附图说明Description of drawings
图1为采用透射电子显微镜TEM模式拍摄的纳米磷灰石颗粒高分辨透射电镜图；Figure 1 is a high-resolution transmission electron microscope image of nano-apatite particles captured by TEM mode of transmission electron microscope;
图2为利用常规检测手段—STEM模式中，图1的磷灰石颗粒打点能谱图；Fig. 2 is the dotted energy spectrogram of the apatite particles of Fig. 1 in the conventional detection method—STEM mode;
图3为透射电镜TEM模式下，图1中磷灰石颗粒打点能谱图；Fig. 3 is the dotted energy spectrum of apatite particles in Fig. 1 under the TEM mode of transmission electron microscope;
图4为图3中粉红框位置放大图；Figure 4 is an enlarged view of the position of the pink box in Figure 3;
图5为本发明的步骤流程图。FIG. 5 is a flow chart of the steps of the present invention.
具体实施方式Detailed ways
为使本发明的目的、技术方案和优点更加清楚，下面本发明中的技术方案进行清楚、完整地描述，显然，所描述的实施例是本发明一部分实施例，而不是全部的实施例。基于本发明中的实施例，本领域普通技术人员在没有作出创造性劳动前提下所获得的所有其他实施例，都属于本发明保护的范围。In order to make the purpose, technical solutions and advantages of the present invention clearer, the technical solutions in the present invention are described clearly and completely below. Obviously, the described embodiments are part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those of ordinary skill in the art without creative efforts shall fall within the protection scope of the present invention.
如图5所示，本发明提供一种透射电镜能谱超分辨分析方法，所述方法包括以下步骤：As shown in Figure 5, the present invention provides a method for super-resolution analysis of transmission electron microscope energy spectrum, the method comprises the following steps:
步骤1.目标样品的选择与分析；Step 1. Selection and analysis of target samples;
步骤2.微量元素组成分析样品的准备；Step 2. Preparation of samples for trace element composition analysis;
步骤3.目标样品的性质与元素组成分析(是否为电子束敏感样品、样品的主量元素和目标微量元素组成)；Step 3. Analysis of the properties and elemental composition of the target sample (whether it is an electron beam sensitive sample, the composition of the major elements of the sample and the target trace elements);
步骤4.根据需要制备透射电子显微镜观察样品；Step 4. Prepare transmission electron microscope observation samples as needed;
步骤5.对上一步制备样品，放入透射电子显微镜进行形貌观察，寻找合适的分析位置；
步骤6.查询相关元素的X射线光电子能谱仪的峰位，重点区别出可能与目标微量元素峰位有干扰的主量元素，并找寻能够与主量元素能谱峰位区别开的微量元素的关键峰位；Step 6. Query the peak positions of the X-ray photoelectron spectrometer of related elements, focus on identifying the major elements that may interfere with the peak positions of the target trace elements, and search for trace elements that can be distinguished from the peak positions of the major elements. The key peak position of ;
步骤7.针对微量元素检测需求，不采用传统的STEM模式进行能谱分析，而采用TEM模式在平行光模式下进行能谱信号采集，极大的提高能谱信号采集量，从而达到在纳米尺度下进行微量元素分析的目的。Step 7. For the detection requirements of trace elements, instead of using the traditional STEM mode for energy spectrum analysis, the TEM mode is used to collect the energy spectrum signal in the parallel light mode, which greatly improves the amount of energy spectrum signal collection, so as to achieve the nanometer scale. for the purpose of trace element analysis.
所述步骤(1)具体包括如下步骤：通过肉眼和显微镜鉴定矿物岩石基本分类；根据矿物岩石类型借助相应化学分析方法确定目标样品的微量元素种类与含量；在完成化学分析后，选择含有感兴趣的微量元素的矿物岩石作为目标样品。The step (1) specifically includes the following steps: identifying the basic classification of minerals and rocks by the naked eye and a microscope; determining the types and contents of trace elements of the target sample by means of corresponding chemical analysis methods according to the types of minerals and rocks; The trace elements of the mineral rock as the target sample.
所述步骤(3)中矿物物相鉴定，形貌观察、元素组成分析方法包括但不限于如下可用于样品表面形貌分析的显微设备；微区X射线衍射方法(微区束斑通常小于100微米)、粉末X射线衍射方法、光学显微镜、扫描电子显微镜、原子力显微镜、ICP-OES、ICP-MS、电子探针、电子能谱、激光剥蚀-电感耦合等离子质谱、二次离子质谱方法。In the step (3), mineral phase identification, morphology observation, and elemental composition analysis methods include but are not limited to the following microscopic equipment that can be used for sample surface morphology analysis; 100 microns), powder X-ray diffraction method, optical microscope, scanning electron microscope, atomic force microscope, ICP-OES, ICP-MS, electron probe, electron spectroscopy, laser ablation-inductively coupled plasma mass spectrometry, secondary ion mass spectrometry methods.
所述步骤(7)中分析方法主要为：①在透射电镜TEM平行光模式下，对目标区域进行长时间特征X射线信号采集，能够极大的提高能谱信号的计数，从而实现对目标微量元素的分析；The analysis method in the step (7) is mainly as follows: 1. In the TEM parallel light mode of the transmission electron microscope, long-time characteristic X-ray signal acquisition is performed on the target area, which can greatly improve the count of the energy spectrum signal, so as to realize the detection of the target trace amount. elemental analysis;
②针对样品的元素组成，根据主量元素与微量元素峰位进行分析，寻找与主量元素峰位不产生重叠的微量元素的峰位；②According to the element composition of the sample, analyze according to the peak positions of major elements and trace elements, and find the peak positions of trace elements that do not overlap with the peak positions of major elements;
③根据特殊形状的分析区域，可以通过调整透射电镜的C2镜来改变光斑的形状来进行能谱信号采集；③According to the analysis area of special shape, the energy spectrum signal can be collected by adjusting the C2 mirror of the transmission electron microscope to change the shape of the spot;
④针对电子束敏感样品，可适当减少电流强度，扩大光斑直径，来进行能谱信号采集。④ For electron beam sensitive samples, the current intensity can be appropriately reduced and the spot diameter can be enlarged to collect energy spectrum signals.
实施例Example
透射电子显微镜在纳米地球科学、材料学等领域应用广泛，因为具有超高空间分辨率，因此是在纳米尺度进行研究的重要工具。图1采用透射电子显微镜TEM模式拍摄的纳米磷灰石颗粒高分辨透射电镜图，能够清楚的看到颗粒形貌及结构，呈现了透射电镜研究纳米矿物的优势。Transmission electron microscopy is widely used in nano-geoscience, materials science and other fields. Because of its ultra-high spatial resolution, it is an important tool for research at the nanoscale. Figure 1. The high-resolution TEM image of nano-apatite particles taken by TEM mode of transmission electron microscope. The morphology and structure of the particles can be clearly seen, showing the advantages of TEM to study nano-minerals.
本实施例阐述了磷灰石中类质同象稀土元素Y的鉴定，一方面通过LA-ICP-MS得出，稀土元素的含量为600ppm左右(0.06wt％)，而能谱的理论检出限位0.1-0.5wt％；另一方面,Y元素常用判别峰位Lα峰位1.92Kev，而主量元素P的K峰位2.02Kev，两者相差0.1Kev，低于能谱的能量分辨率0.13Kev，因此不能判断，所以需要用Y元素K峰14.93Kev来判别。This example describes the identification of isomorphic rare earth element Y in apatite. On the one hand, it is obtained by LA-ICP-MS that the content of rare earth element is about 600ppm (0.06wt%), and the theoretical detection of energy spectrum The limit is 0.1-0.5wt%; on the other hand, the Lα peak position of the Y element is usually 1.92Kev, while the K peak position of the main element P is 2.02Kev, the difference between the two is 0.1Kev, which is lower than the energy resolution of the energy spectrum. 0.13Kev, so it cannot be judged, so it is necessary to use the Y element K peak of 14.93Kev to judge.
根据图2和图4，图2为利用常规检测手段—STEM模式中图1的磷灰石颗粒打点能谱图，图4为透射电镜TEM模式下，图1中磷灰石颗粒打点能谱图。通过常规方法和本发明方法的能谱图计数对比，本发明方法为常规方法的1.5万倍。通过对比图3和图5，图3为图2中13.5KeV-16.5KeV能量位置放大图，而图5为图4中13.5KeV-16.5KeV能量位置放大图，可以看出本发明方法能够很好的检测出磷灰石中Y元素的信号，实现了微量元素Y元素的分析检测，而常规方法打点分析方法不能达到要求。According to Fig. 2 and Fig. 4, Fig. 2 is the dotted energy spectrum of the apatite particles in Fig. 1 using the conventional detection method-STEM mode, and Fig. 4 is the dotted energy spectrum of the apatite particles in Fig. 1 under the TEM mode of the transmission electron microscope. . By comparing the energy spectrum counts between the conventional method and the method of the present invention, the method of the present invention is 15,000 times that of the conventional method. By comparing Fig. 3 and Fig. 5, Fig. 3 is an enlarged view of the energy position of 13.5KeV-16.5KeV in Fig. 2, while Fig. 5 is an enlarged view of the energy position of 13.5KeV-16.5KeV in Fig. 4, it can be seen that the method of the present invention can be very good The signal of Y element in apatite is detected by the method, and the analysis and detection of trace element Y element is realized, but the conventional method of dot analysis method cannot meet the requirements.
当尝试提高STEM打点分析时间，但因透射样品较薄，而天然样品相对不稳定，短时间内就会被击穿，一是破坏样品；二是获取不了较高的信号量。当尝试对比利用STEM-Mapping来进行分析，通过长时间Mapping也能够获取很高的计数，但是花费的时间约为该发明方法的10倍，效率较低。When trying to increase the STEM dot analysis time, but because the transmission sample is thin, and the natural sample is relatively unstable, it will be broken down in a short time. First, the sample will be destroyed; second, a higher signal amount cannot be obtained. When trying to compare the use of STEM-Mapping for analysis, high counts can also be obtained by long-time Mapping, but the time spent is about 10 times that of the method of the invention, and the efficiency is low.
最后应说明的是：以上实施例仅用以说明本发明的技术方案，而非对其限制；尽管参照前述实施例对本发明进行了详细的说明，本领域的普通技术人员应当理解：其依然可以对前述各实施例所记载的技术方案进行修改，或者对其中部分技术特征进行等同替换；而这些修改或者替换，并不使相应技术方案的本质脱离本发明各实施例技术方案的精神和范围。Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention, but not to limit them; although the present invention has been described in detail with reference to the foregoing embodiments, those of ordinary skill in the art should understand that it can still be The technical solutions described in the foregoing embodiments are modified, or some technical features thereof are equivalently replaced; and these modifications or replacements do not make the essence of the corresponding technical solutions deviate from the spirit and scope of the technical solutions of the embodiments of the present invention.
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| CN104181175A (en) * | 2014-07-18 | 2014-12-03 | 中山大学 | Water particle geochemical prospecting method and application thereof |
| EP3121834A1 (en) * | 2015-07-23 | 2017-01-25 | FEI Company | Fiducial formation for tem/stem tomography tilt-series acquisition and alignment |
| CN106480195A (en) * | 2016-10-21 | 2017-03-08 | 中国科学院地质与地球物理研究所 | The method that the combination of fluorescent electronic microscope is identified to microorganism and mineralising is analyzed |
| CN110793991A (en) * | 2019-10-12 | 2020-02-14 | 国家地质实验测试中心 | Analytical method for occurrence state of Re in sedimentary rock |
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| CN104181175A (en) * | 2014-07-18 | 2014-12-03 | 中山大学 | Water particle geochemical prospecting method and application thereof |
| EP3121834A1 (en) * | 2015-07-23 | 2017-01-25 | FEI Company | Fiducial formation for tem/stem tomography tilt-series acquisition and alignment |
| CN106480195A (en) * | 2016-10-21 | 2017-03-08 | 中国科学院地质与地球物理研究所 | The method that the combination of fluorescent electronic microscope is identified to microorganism and mineralising is analyzed |
| CN110793991A (en) * | 2019-10-12 | 2020-02-14 | 国家地质实验测试中心 | Analytical method for occurrence state of Re in sedimentary rock |
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