JPH0656361B2 - Quantitative analysis method for layered samples by optical emission spectroscopy - Google Patents
Quantitative analysis method for layered samples by optical emission spectroscopyInfo
- Publication number
- JPH0656361B2 JPH0656361B2 JP59037109A JP3710984A JPH0656361B2 JP H0656361 B2 JPH0656361 B2 JP H0656361B2 JP 59037109 A JP59037109 A JP 59037109A JP 3710984 A JP3710984 A JP 3710984A JP H0656361 B2 JPH0656361 B2 JP H0656361B2
- Authority
- JP
- Japan
- Prior art keywords
- sample
- emission
- evaporation
- evaporation amount
- quantitative analysis
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/66—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence
- G01N21/67—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light electrically excited, e.g. electroluminescence using electric arcs or discharges
Landscapes
- Health & Medical Sciences (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Physics & Mathematics (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Investigating, Analyzing Materials By Fluorescence Or Luminescence (AREA)
Description
【発明の詳細な説明】 イ．産業上の利用分野 本発明はグロー放電によつて試料面を削除しながら深さ
方向に分析を進めて行く発光分光分析で多層メツキ等の
付着量を測定する分析方法に関する。Detailed Description of the Invention a. BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an analysis method for measuring the amount of multi-layered metal deposits or the like by emission spectroscopic analysis in which analysis is advanced in the depth direction while deleting the sample surface by glow discharge.
ロ．従来技術 試料をグロー放電管の陰極にして、陰極スパツタリング
によつて試料面を削りながら蒸発した試料原子をグロー
放電で発光させる発光分析法は試料面の深さ方向の成分
変化を分析できる特徴があるが、従来は定性的な分析し
かできなかつた。例えば鉄地亜鉛メツキを分析すると、
当初亜鉛の発光が強く鉄の発光が弱くて、時間が経つと
鉄の発光が強くなり亜鉛の発光が弱くなる。これは亜鉛
のメツキ層が次第に揮発し去つて鉄地が出て来るからで
あるが、各元素の発光強度の時間的な変化の記録で、単
純に発光強度軸を元素濃度に、時間軸を試料表面からの
深さに読み替えることができれば、定量分析になるので
あるが、両軸を元素濃度，深さに換算する適当な操作が
見当らず、定量分析ができなかつた。B. A conventional technique is to use a sample as the cathode of a glow discharge tube, and the emission analysis method in which vaporized sample atoms are emitted by glow discharge while scraping the sample surface by cathode sputtering is characterized by the ability to analyze component changes in the depth direction of the sample surface. However, in the past, only qualitative analysis was possible. For example, if you analyze iron-based zinc plating,
Initially, zinc emission is strong and iron emission is weak. Over time, iron emission is strong and zinc emission is weak. This is because the zinc plating layer gradually evaporates away and the iron material comes out, but it is a record of the temporal change of the emission intensity of each element, and the emission intensity axis is simply the element concentration and the time axis is the If the depth from the surface of the sample could be read, quantitative analysis would be possible, but there was no suitable operation for converting both axes into element concentration and depth, and quantitative analysis could not be performed.
ハ．目 的 本発明は発光強度及び時間から元素濃度及び深さを算出
する方法を与え、グロー放電発光分光分析で試料面の深
さ方向の定量分析を可能にしようとするものである。C. Aim The present invention provides a method for calculating element concentration and depth from luminescence intensity and time, and makes it possible to perform quantitative analysis in the depth direction of a sample surface by glow discharge emission spectroscopy.
ニ．構 成 今第１図に示すような発光強度の時間記録が得られたと
する。この図でＡはＡ元素の発光強度、ＢはＢ元素の発
光強度を示す。この結果は定性的には試料表面はＡ元素
で覆われ、両元素の混合層があつて下地はＢ元素である
と云うことを物語つている。この図で斜線を入れた部分
の面積は時間ｔ１，ｔ２間のＡ元素の蒸発量に関係して
いる。また発光強度はその時点でのＡ元素の蒸発速度に
関係している。同様の関係はＢ元素についても成立つて
いる。そこで一般に発光強度曲線の時間ｔ１，ｔ２間の
面積をＳとすると、この時間内における元素蒸発量Ｗは
Ｗ＝ｆ(S)と書ける。標準試料を用いてｆ(S)の形を求め
ておく。第１図においてｔ１，ｔ２時間の間のＡ元素の
発光強度曲線の面積をＳａ，同じくＢ元素の面積をＳｂ
とし、夫々の蒸発量の面積関数をｆａ(S)及びｆｂ(S)と
すると、この関数からｔ１，ｔ２間のＡ，Ｂ両元素の蒸
発量が求まる。これをＷａ，Ｗｂとすると、時間ｔ１，
ｔ２間において露出していた試料面の組成は Ａ元素 Ｗａ／（Ｗａ＋Ｗｂ） Ｂ元素 Ｗｂ／（Ｗａ＋Ｗｂ） となる。この組成の合金の比重をｇ、試料面積をσとす
ると、 （Ｗａ＋Ｗｂ）／ｇσ によつて時間ｔ１，ｔ２の間に削られた試料面の深さｄ
が求まる。この操作を第１図で時間０の点から時間幅を
適当に区切つて行くと、各区分毎の組成比及び削れ深さ
が求められて、第２図のような深さ方向のＡ，Ｂ両元素
の組成比の変化を示すすグラフを画くことができる。D. Composition It is assumed that the time record of the emission intensity as shown in Fig. 1 is obtained. In this figure, A indicates the emission intensity of the A element, and B indicates the emission intensity of the B element. This result qualitatively shows that the sample surface is covered with the A element, the mixed layer of both elements is present, and the underlayer is the B element. The area of the shaded portion in this figure is related to the evaporation amount of the element A between times t1 and t2. Further, the emission intensity is related to the evaporation rate of the element A at that time. The same relationship holds for the B element. Therefore, generally, assuming that the area between the times t1 and t2 of the emission intensity curve is S, the element evaporation amount W within this time can be written as W = f (S). The shape of f (S) is obtained using a standard sample. In FIG. 1, the area of the emission intensity curve of the A element between t1 and t2 hours is Sa, and the area of the B element is Sb.
Assuming that the area functions of the respective evaporation amounts are fa (S) and fb (S), the evaporation amounts of both elements A and B between t1 and t2 can be obtained from this function. If this is Wa and Wb, the time t1,
The composition of the exposed sample surface during t2 is A element Wa / (Wa + Wb) B element Wb / (Wa + Wb). If the specific gravity of the alloy of this composition is g and the sample area is σ, the depth d of the sample surface cut between the times t1 and t2 by (Wa + Wb) / gσ
Is required. By appropriately dividing the time width from the point of time 0 in Fig. 1 in Fig. 1, the composition ratio and shaving depth of each segment are obtained, and A, B in the depth direction as shown in Fig. 2 are obtained. It is possible to draw a graph showing the change in the composition ratio of both elements.
ホ．実施例 関数ｆの形をaS3＋bS3＋cS＋ｄの形で近似し、係数ａ，
ｂ，ｃ，ｄを各元素毎に標準試料によつて決定してお
く。E. Example The form of the function f is approximated by the form of aS 3 + bS 3 + cS + d, and the coefficient a,
b, c and d are determined for each element by using a standard sample.
第３図は三層メツキが施された試料の分析結果である。
定性分析によつて、第１層はＣｒメツキ、第２層はＦ
ｅ，Ｚｎ合金メツキ、第３層はＮｉ，Ｚｎの合金メツキ
で素地はＦｅと見当がついている。そこでこれら各元素
について前記関数の各係数を決めておく。第３図でＣｒ
はクロム、Ｆｅは鉄、Ｚｎは亜鉛、Ｎｉはニツケルの発
光強度曲線である。図で矢イ，ロ，ハは夫々クロム、
鉄，亜鉛の夫々の曲線の半値幅の点で、この点の所が各
層の境界であると見て、時間０からｔ１まで、ｔ１から
ｔ２まで、ｔ２からｔ３までの各時間帯における各発光
強度曲線の面積を求めて、各層における各元素の蒸発量
を求め、それから各元素の組成比を算出し、各層の蒸発
総量とその組成比の合金の比重とから各層の厚さを算出
し、メツキ層の厚さ方向の組成変化に変換して画いたの
が第４図である。FIG. 3 shows the analysis results of the sample with the three-layer plating.
Qualitative analysis shows that the first layer is Cr plating and the second layer is F
e, Zn alloy plating, the third layer is Ni, Zn alloy plating, and the base material is assumed to be Fe. Therefore, each coefficient of the function is determined for each of these elements. In Figure 3, Cr
Is chromium, Fe is iron, Zn is zinc, and Ni is nickel emission intensity curve. In the figure, arrows a, b and c are chrome,
At the half-width value of each curve of iron and zinc, it is assumed that this point is the boundary of each layer, and each light emission in each time zone from time 0 to t1, t1 to t2, and t2 to t3. Obtain the area of the strength curve, determine the evaporation amount of each element in each layer, calculate the composition ratio of each element from it, calculate the thickness of each layer from the total evaporation amount of each layer and the specific gravity of the alloy of the composition ratio, FIG. 4 is a diagram in which the composition change in the thickness direction of the plating layer is converted and drawn.
上述実施例では関数ｆ(S)の形を３次多項式で表わした
が、この式の形は任意であり、この形で表わすとコンピ
ユータによる演算のプログラムが簡単になる。また上述
実施例は発光強度曲線の面積と蒸発量との間の関数形を
求めて、蒸発量を決定し、蒸発量から層の深さを算出し
ているが、発光強度の瞬時値Ｉと蒸発速度Ｗとの関係を
予め求めておいて、各時点における蒸発速度から組成を
決定し、組成から比重を求めて、各時点における試料面
の削れ速さを求めて、深さ方向の組成変化を画くことも
可能である。In the above-mentioned embodiment, the form of the function f (S) is represented by a cubic polynomial, but the form of this formula is arbitrary, and this form simplifies the program for calculation by the computer. Further, in the above-described embodiment, the functional form between the area of the emission intensity curve and the evaporation amount is obtained, the evaporation amount is determined, and the layer depth is calculated from the evaporation amount. The relationship with the evaporation rate W is obtained in advance, the composition is determined from the evaporation rate at each time point, the specific gravity is calculated from the composition, the scraping speed of the sample surface at each time point is calculated, and the composition change in the depth direction. It is also possible to draw.
ヘ．効 果 グロー放電発光分光分析では、同じ元素であつてもメツ
キ条件の違い等によつて蒸発速度がかなり異り、従つて
発光強度も異る。このため発光強度即その元素の含有量
と云うわけに行かない。蒸発速度が異るから時間経過が
深さ方向の距離と一義的に対応していない。強い発光強
度で継続時間が短いのはその元素が多くて層厚が薄く、
弱い発光で継続時間が長いのはその元素が少く層厚が厚
いと云うことにはならない。一方は蒸発速度が速く、他
方は蒸発速度が遅いのである。F. EFFECTS In glow discharge emission spectroscopy, even with the same element, the evaporation rate differs considerably due to differences in the plating conditions, and the emission intensity also differs accordingly. Therefore, it cannot be said that the content of the element is the same as the emission intensity. Since the evaporation rate is different, the passage of time does not uniquely correspond to the distance in the depth direction. The strong emission intensity and short duration are due to the large number of elements and the thin layer thickness.
The weak emission and long duration do not mean that the element is small and the layer thickness is large. One has a high evaporation rate and the other has a low evaporation rate.
本発明では発光強度曲線の面積によつて蒸発量を求める
ようにしたので、蒸発速度のばらつきの影響を受けず、
試料面の深さ方向の定量分析が可能となつた。In the present invention, since the amount of evaporation is obtained by the area of the emission intensity curve, it is not affected by variations in evaporation rate,
Quantitative analysis in the depth direction of the sample surface became possible.
第１図は本発明の原理を説明するためのグラフ、第２図
は本発明によつて得られる結果を説明するグラフ、第３
図は本発明方法を実行した分析例のグラフ、第４図は第
３図の分析結果を本発明方法により解析した結果を示す
グラフである。FIG. 1 is a graph for explaining the principle of the present invention, FIG. 2 is a graph for explaining the results obtained by the present invention, and FIG.
FIG. 4 is a graph of an analysis example in which the method of the present invention is executed, and FIG. 4 is a graph showing the results of analysis of the analysis results of FIG. 3 by the method of the present invention.
Claims (1)
を揮散させながら試料面の深さ方向に分析を進めて行く
発光分光分析において、試料を構成する各元素の発光強
度の時間的変化を記録し、発光強度とそのときの元素の
蒸発速度或は発光光度曲線の或る時間幅の面積とその時
間幅内のその元素の蒸発量との関係を標準試料によって
予め求めておき、これを用いて上記試料の各元素の発光
光度曲線から各元素の蒸発量を求め、この蒸発量から各
元素同士の比率を算出し、その組成の物質の比重と全元
素の蒸発量の総和とから、試料表面の削れ量を算出し
て、各元素の深さ方向の分布を求めることを特徴とする
発光分光分析による層状試料の定量分析方法。1. In an emission spectroscopic analysis in which an analysis proceeds in the depth direction of the sample surface while volatilizing the surface of the sample with a glow discharge tube having the sample as a cathode, a temporal change in the emission intensity of each element constituting the sample. The relationship between the emission intensity and the evaporation rate of the element at that time or the area of a certain time width of the emission light intensity curve and the evaporation amount of the element within that time width is obtained in advance using a standard sample. Obtain the evaporation amount of each element from the emission light curve of each element of the sample using, calculate the ratio of each element from this evaporation amount, from the specific gravity of the substance of that composition and the total evaporation amount of all elements A quantitative analysis method for a layered sample by optical emission spectroscopy, which comprises calculating the amount of abrasion of the sample surface and obtaining the distribution of each element in the depth direction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59037109A JPH0656361B2 (en) | 1984-02-28 | 1984-02-28 | Quantitative analysis method for layered samples by optical emission spectroscopy |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| JP59037109A JPH0656361B2 (en) | 1984-02-28 | 1984-02-28 | Quantitative analysis method for layered samples by optical emission spectroscopy |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| JPS60179633A JPS60179633A (en) | 1985-09-13 |
| JPH0656361B2 true JPH0656361B2 (en) | 1994-07-27 |
Family
ID=12488430
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| JP59037109A Expired - Fee Related JPH0656361B2 (en) | 1984-02-28 | 1984-02-28 | Quantitative analysis method for layered samples by optical emission spectroscopy |
Country Status (1)
| Country | Link |
|---|---|
| JP (1) | JPH0656361B2 (en) |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3996817B2 (en) * | 2002-08-27 | 2007-10-24 | 株式会社堀場製作所 | Glow discharge analyzer and analysis result display method of glow discharge analyzer |
| JP5754297B2 (en) * | 2011-08-18 | 2015-07-29 | Ｊｆｅスチール株式会社 | Thickness uniformity evaluation method |
| RU2647533C1 (en) * | 2016-10-06 | 2018-03-16 | Валентин Николаевич Аполицкий | Method of identification, diagnostics and evaluation of a substance quality using the integral scintillation method of substance investigation |
-
1984
- 1984-02-28 JP JP59037109A patent/JPH0656361B2/en not_active Expired - Fee Related
Non-Patent Citations (1)
| Title |
|---|
| 日本金属学会誌第４７巻第１０号（１９８３）Ｐ．８４４−８４９ |
Also Published As
| Publication number | Publication date |
|---|---|
| JPS60179633A (en) | 1985-09-13 |
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| Date | Code | Title | Description |
|---|---|---|---|
| LAPS | Cancellation because of no payment of annual fees |