CN1297812C - Resistance change rate detection method for corrosion-resisting properties of thin film material and device - Google Patents
Resistance change rate detection method for corrosion-resisting properties of thin film material and device Download PDFInfo
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Abstract
一种薄膜材料及器件耐腐蚀性能的电阻变化率检测方法，将薄膜试样的测试表面浸泡在所配制模拟海洋性气候环境的腐蚀介质溶液中，试样在腐蚀过程中，与腐蚀介质接触表面的微观组织状态发生变化或发生腐蚀剥离，造成该尺寸区域材料有效导电层厚度改变，从而引起其电阻的变化，测量从浸泡起始后试样电阻随时间的变化率，根据变化率就可以反映薄膜材料及器件的耐腐蚀性能和长期使用可靠性。本发明能够方便可靠的检测薄膜材料的耐腐蚀性能，而无需复杂的仪器设备，不仅可以进行不同材料、不同腐蚀介质(种类、浓度、温度)的比较研究，而且可以对材料的长期使用可靠性做出预测。同时也可以与其它现有模拟环境腐蚀试验装置结合起来使用。
A resistance change rate detection method for the corrosion resistance of thin film materials and devices. The test surface of the thin film sample is soaked in the prepared corrosive medium solution simulating the marine climate environment. Changes in the microstructure state of the sample or corrosion and peeling occur, resulting in a change in the thickness of the effective conductive layer of the material in this size area, thereby causing a change in its resistance. Measure the change rate of the sample resistance with time from the beginning of immersion, and it can be reflected according to the change rate Corrosion resistance and long-term reliability of thin film materials and devices. The invention can conveniently and reliably detect the corrosion resistance of thin film materials without complex instruments and equipment, not only can carry out comparative research on different materials and different corrosive media (types, concentrations, temperatures), but also can check the long-term use reliability of materials make predictions. At the same time, it can also be used in combination with other existing simulated environmental corrosion test devices.
Description
Technical field
What the present invention relates to is a kind of method that is used to corrode the detection film performance in detection technique field, specifically is the resistance change rate detection method of a kind of membraneous material and device decay resistance.
Background technology
Membraneous material and utilize the various components and parts of its preparation to be widely used in microelectronic device, integrated circuit, electronic package material and use occasion that some are special.These materials and device use in different surrounding mediums according to actual operating conditions, such as hygrothermal environment, different climatic environment (ocean, industry, coastal waters industry), soda acid chemical environment and some other harsh environment for use, therefore need to detect membraneous material and the decay resistance of device in the corrosion environment medium and long-term dependability.Up to now, the method that detects membraneous material and device corrosive nature mainly contains: (1) image viewing method: sample is exposed in the specific corrosive medium, observes the development of defective or corrosion product by microscope or other technology.The shortcoming of this method is that quantitative evaluation needs some special technique and equipment, and it is bigger influenced by human factor; (2) gravimetric method: for the comparatively tangible material of weight change in the corrosion process, this method can reflect material corrosion resistance preferably.But, because its thin layer weight is very little and corrosion process is inhomogeneous, thereby obtain relatively difficulty of quantitative data, and the instrument of weighing is had relatively high expectations for membraneous material; (3) electrochemical method: decay resistance and mechanism that can very fast reflection material, shortcoming is to make prediction to the long-term dependability of material; (4) measure the variation in thickness method: the method for material corrosion speed is evaluated in the variation of thickness in corrosion process by MEASUREMENTS OF THIN or coating.But because the unevenness and the corrosion process of the own thickness of film or coating material surface are inhomogeneous, thereby it is bigger influenced by equipment and human factor.
Find by prior art documents, M.Tenhover etc. are in " Materials Science andEngineering " (Materials Science and Engineering, 1988, Vol.99,483～487) in " the Corrosionresistance and passive layer formation in amorphous binary Cr alloys " that delivers on (decay resistance of binary amorphous evanohm and the passivation layer form) paper, use surface profiler to measure in different etchant solutions film thickness over time, comparative studies the Cr-Si of magnetron sputtering method preparation, Cr-B, (Cr, Ni)-Si film decay resistance.Consider that the film surface corrosion is inhomogeneous in the influence of film surface thickness offset, film substrate surfaceness of sputtering method preparation and the corrosion process, when therefore adopting this method, it is bigger influenced by surveying instrument and human factor.Particularly for good materials of decay resistance such as Cr-Si films, the cycle that the acquisition data need is also long.
Summary of the invention
The object of the invention is to overcome the deficiencies in the prior art and limitation, the resistance change rate detection method of a kind of membraneous material and device decay resistance is provided, make it pass through MEASUREMENTS OF THIN material and device resistance rate (Δ R/R) over time in different severe rugged environment media, just can reflect the requirement that material corrosion resistance and long-term dependability are predicted according to Δ R/R, have simple characteristics.
The present invention is achieved by the following technical solutions, with the test surfaces of film sample be immersed in prepare in the corrosive medium solution of simulation ocean climate environment, because membraneous material and device are in corrosion process, can change or take place corrosion with the microstructure state of corrosive medium surface in contact peels off, cause the effective conductive layer thickness of this size area material to change, thereby cause its changes in resistance, measurement just can reflect the decay resistance and the long-term dependability of membraneous material and device from soaking initial back sample resistance rate over time according to resistance change rate.
Below the inventive method is further described, concrete steps are as follows:
(1) sample is prepared: select for use resistance value to be respectively the film sample of 400 ± 5 Ω and 520 ± 5 Ω, the control sample thin layer has identical thickness and surface area, and the protection of JW-1 type epoxy sealing is used at lead-in wire position, sample two ends;
(2) corrosive medium solution preparation: the employing mass percent concentration is 3.5% NaCl simulation ocean climate environment.At the corrosive medium of other environment, then adopt 3.5% Na
2SO
4The NaOH of solution, 0.1M, HCl solution divide simulation industrialness climatic environment, alkalescence and acid environment for use.After solution allocation is good, it is held in the airtight container;
(3) working temperature: the selection work temperature is respectively 25 ℃ and 45 ℃.Adjust the corrosive medium solution temperature and after the setting working temperature, keep constant temperature, then sample is soaked into prepare in the corrosive medium solution;
(4) resistance change rate is measured: by digital DC bridge measurement sample from soaking the rate of change (Δ R/R) of initial back sample resistance along with the time.Under identical time conditions, when different thin film compositions, different etchant solution (kind, concentration, temperature) contrast, the sample that Δ R/R is little has better decay resistance and long-term dependability.
The invention has the advantages that the limitation that has overcome existing membraneous material and device corrosion behavior assessment technique.Test method is easily gone, and test unit is simple, not only can be used for the comparative study of different materials, different corrosive medium (kind, concentration, temperature), and can satisfy the requirement that the long-term dependability of material is made prediction.Simultaneously also can combine use with other existing simulated environment corrosion testing apparatus.For membraneous material and device production enterprise, adopt the inventive method, not only can overcome the testing tool that prior art brings and require shortcomings such as height, equipment cost height, personnel's technical requirement height, data reliability deficiency, and can utilize more existing measurement of correlation devices, transform a little, very the testing film material of intuitive and convenient and the corrosive power of anti-surrounding medium of device.The present invention also extends to other corrosion or oxidation rate is lower, have the various materials field of conductive capability.
Description of drawings
Fig. 1 embodiment of the invention equipment therefor structural representation;
Fig. 2 Cr-Si-Ni resistance film sample is resistance change rate and time relation in ocean of simulating and industrial environment;
Fig. 3 Cr-Si-Ni resistance film sample is resistance change rate and time relation in acid and alkaline corrosion medium;
Fig. 4 Cr-Si-Ni and Cr-Si-Ni-Al resistance film sample resistance change rate and time relation in the alkaline corrosion medium;
Fig. 5 solution concentration is to the influence of Cr-Si-Ni-Al resistance film sample resistance change rate;
Fig. 6 temperature is to the influence of Cr-Si-Ni-Al resistance film sample resistance change rate.
Embodiment
Below in conjunction with drawings and Examples technical scheme of the present invention is further described.
Use the present invention and examined widely used Cr-Si-Ni and corrosion behavior and the long-term reliability of Cr-Si-Ni-Al thin film resistor in the varying environment medium in the electronics industry.Present embodiment has mainly been investigated before making thin film resistor, the decay resistance of film itself, purpose is in order to check in the ocean of simulating, industry, acidity, alkaline environment medium, thin film composition, surrounding medium solution kind, concentration and temperature are made prediction to its long-term dependability simultaneously to effect on corrosion.
Cr-Si-Ni and Cr-Si-Ni-Al film use homemade casting alloy target, and (the target composition is respectively Cr
38Si
55Ni
7And Cr
36Si
52Ni
6.5Al
5.5), adopt the magnetically controlled sputter method preparation.Use identical preparation technology parameter, thereby guarantee the thickness basically identical of film.Thin film deposition is at φ 3.5 * 10mm Al
2O
3On the ceramic bases, to get rid of the influence of substrate to corrosion.The sample of preparing was 500 ℃ of thermal treatments of chamber type electric resistance furnace 180 minutes.Sampling and measuring shows, this moment sample temperature-coefficient of electrical resistance (TCR) at ± 50ppm/ ℃, satisfied of the basic demand of used in electronic industry thin film resistor to TCR.For the ease of the decay resistance of further duplicate, with sample two ends pressure cap, the welding lead after the thermal treatment, the sheet resistance of selecting for use is respectively 400 ± 5 Ω (Cr-Si-Ni film) and 520 ± 5 Ω (Cr-Si-Ni-Al film).With the protection of JW-1 type epoxy sealing, attention will guarantee that the area of test surfaces of each sample is identical with the sample picked out lead-in wire position, and adopting the thickness of film among the present invention is 100nm, surface area 0.6cm
2In the present embodiment, with reference to " the basic environmental test rules of electric and electronic product " (GB2423.17-81), the employing weight percent concentration is 3.5% NaCl, Na
2SO
4Solution is simulated ocean and the industrial environment in the actual environment for use respectively, adopts NaOH, the HCl solution of 0.1M to represent acidity and alkaline environment for use respectively.By test unit shown in Figure 1, wherein sample 1, lead-in wire 2, closed container 3, etchant solution 4, constant water bath box 5, digital DC electric bridge 6, with reference to " classification of electric and electronic product environmental parameter and harsh grading thereof " (GB4796-84), after adjusting etchant solution temperature to 25 ℃ and 45 ℃ respectively, sample is soaked in the corrosive medium solution for preparing, and soak time is 120h.Use QJ-84 type digital DC bridge measurement sample from soaking the resistance value of each time point after initial, after reaching the soak time of setting, the gained data reduction is become resistance change rate (Δ R/R) over time, just can characterize out Cr-Si-Ni and decay resistance and the long-term dependability (Fig. 2, Fig. 3, Fig. 4, Fig. 5, Fig. 6) of Cr-Si-Ni-Al resistance film in different simulation corrosion environments.
According to Fig. 2 as can be seen, during 120h the Cr-Si-Ni film the Δ R/R under the ocean climate environmental baseline less than industrialness climatic environment condition under Δ R/R, illustrate that the Cr-Si-Ni film has better decay resistance and long-term dependability in ocean climate; Equally according to Fig. 3, under the acid medium condition, the Δ R/R of Cr-Si-Ni film is much smaller than the Δ R/R of film under alkaline medium condition during 120h, so film has better decay resistance and long-term dependability in acid medium.According to Fig. 4, under the alkaline corrosion ambient condition, Cr-Si-Ni film Δ R/R is 2 times of Cr-Si-Ni-Al film Δ R/R during 120h, illustrates in the Cr-Si-Ni film to add after the Al element that the decay resistance of film is greatly improved.According to Fig. 5 and Fig. 6 as can be seen, along with the increase of solution concentration and temperature, the corrosion rate of Cr-Si-Ni-Al film is accelerated.As seen, solution concentration and serviceability temperature have very big influence to the decay resistance of film.
Claims (4)
1. the resistance change rate detection method of membraneous material and device decay resistance, it is characterized in that, the test surfaces of membraneous material and device is immersed in the same temperature solution of corrosive medium of the simulation ocean climate environment of preparing, membraneous material and device are in corrosion process, change with the microstructure state of corrosive medium surface in contact or this surface in contact corrosion takes place is peeled off, cause the effective conductive layer thickness of this surface in contact material to change, thereby cause its changes in resistance, measurement changes rate of change Δ R/R in time from soaking initial back sample resistance, just can reflect the decay resistance and the long-term dependability of membraneous material and device according to this rate of change.
2. the resistance change rate detection method of membraneous material according to claim 1 and device decay resistance is characterized in that, below by step to its further qualification:
(1) sample is prepared: select film sample for use, the control sample thin layer has identical thickness and surface area, and the epoxy sealing protection is used at lead-in wire position, sample two ends;
(2) corrosive medium solution preparation: the employing mass percent concentration is 3.5% NaCl simulation ocean climate environment, after solution allocation is good, it is held in the airtight container;
(3) working temperature: the selection work temperature is respectively 25 ℃ and 45 ℃, adjusts the corrosive medium solution temperature and keep constant temperature after the setting working temperature, then sample is soaked into prepare in the corrosive medium solution;
(4) resistance change rate is measured: by digital DC bridge measurement sample from soaking the variation of initial back sample resistance value, be converted into resistance then and change rate of change Δ R/R in time, under identical time conditions, resistance changes the little sample of rate of change Δ R/R in time and has better decay resistance and long-term dependability.
3. according to the resistance change rate detection method of claim 1 or 2 described membraneous materials and device decay resistance, it is characterized in that, select for use resistance value to be respectively the film sample of 400 ± 5 Ω and 520 ± 5 Ω.
4. the resistance change rate detection method of membraneous material according to claim 2 and device decay resistance is characterized in that, described corrosive medium adopts 3.5% Na
2SO
4The HCl solution corrosion medium of the NaOH of solution, 0.1M, 0.1M is simulated industrialness climatic environment, alkalescence and acid environment for use respectively.
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| JP6362920B2 (en) | 2014-05-16 | 2018-07-25 | 株式会社日立製作所 | Corrosion environment monitoring apparatus and method |
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| CN108627451A (en) * | 2018-04-26 | 2018-10-09 | 深圳大学 | A kind of tester for simulating the effect of multi-state littoral environment |
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| CN113720881A (en) * | 2021-08-23 | 2021-11-30 | 西安热工研究院有限公司 | On-line monitoring method for corrosion depth of boiler heating surface based on resistance measurement |
| CN115493996A (en) * | 2022-08-31 | 2022-12-20 | 广州市南沙区贝科耐蚀新材料研究院 | A real-time monitoring device for pitting corrosion of metal materials |
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| JPH0829341A (en) * | 1994-07-18 | 1996-02-02 | Yoshiki Uragami | Quantitative evaluation of deterioration of resin by ft-ir analysis |
| JPH08320286A (en) * | 1995-05-25 | 1996-12-03 | Matsushita Electric Ind Co Ltd | Thin film evaluation method and its evaluation device |
| JPH0954061A (en) * | 1995-08-11 | 1997-02-25 | Matsushita Electric Ind Co Ltd | Method for evaluating film quality of Al-Cu alloy thin film |
| JP2002139416A (en) * | 2000-10-31 | 2002-05-17 | Hitachi Ltd | Corrosion sensor |
| JP2002350329A (en) * | 2001-05-30 | 2002-12-04 | Hitachi Ltd | Corrosion sensor |
-
2004
- 2004-11-18 CN CNB2004100842970A patent/CN1297812C/en not_active Expired - Fee Related
Patent Citations (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| GB2118309A (en) * | 1982-04-13 | 1983-10-26 | Univ Manchester | Apparatus for monitoring loss of metal by corrosion |
| US5243298A (en) * | 1991-11-04 | 1993-09-07 | Teledyne Ryan Aeronautical, Division Of Teledyne Industries, Inc. | Corrosion monitor by creating a galvanic circuit between an anode wire and a test structure |
| JPH07333188A (en) * | 1994-06-10 | 1995-12-22 | Nakabootec:Kk | Polarization resistance measuring method of under-film metal and polarization resistance measuring sensor therefor |
| JPH0829341A (en) * | 1994-07-18 | 1996-02-02 | Yoshiki Uragami | Quantitative evaluation of deterioration of resin by ft-ir analysis |
| JPH08320286A (en) * | 1995-05-25 | 1996-12-03 | Matsushita Electric Ind Co Ltd | Thin film evaluation method and its evaluation device |
| JPH0954061A (en) * | 1995-08-11 | 1997-02-25 | Matsushita Electric Ind Co Ltd | Method for evaluating film quality of Al-Cu alloy thin film |
| JP2002139416A (en) * | 2000-10-31 | 2002-05-17 | Hitachi Ltd | Corrosion sensor |
| JP2002350329A (en) * | 2001-05-30 | 2002-12-04 | Hitachi Ltd | Corrosion sensor |
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