CN1657911A - Testing method for water oxygen permeability and its testing equipment - Google Patents

Testing method for water oxygen permeability and its testing equipment Download PDF

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Publication number
CN1657911A
CN1657911A CN 200510051425 CN200510051425A CN1657911A CN 1657911 A CN1657911 A CN 1657911A CN 200510051425 CN200510051425 CN 200510051425 CN 200510051425 A CN200510051425 A CN 200510051425A CN 1657911 A CN1657911 A CN 1657911A
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layer
oxygen permeability
water oxygen
sample
encapsulated layer
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CN100507510C (en
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邱勇
吴朝新
王立铎
高裕弟
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Tsinghua University
Beijing Visionox Technology Co Ltd
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Tsinghua University
Beijing Visionox Technology Co Ltd
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Abstract

The invention relates to a testing method for water oxygen permeability and its testing equipment, which is aimed at simplifying testing method and reducing harsh requirement for the testing equipment. The invention measures time reflectivity variation of two different samples packed with active metallic layer, and estimates the water oxygen permeability of substrate layer or package layer according to formula B=dR/dt proportional to (V[substrate layer] + V[package layer]). The testing equipment is comprised by light source, polaroid sheet, plate glass, three photoelectric detectors, data collection system, computer, one second splitting tablet. The testing method and its testing equipment can measure water oxygen permeability for various materials.

Description

A kind of method of testing of water oxygen permeability and testing apparatus thereof
Technical field
The present invention relates to a kind of method of testing and testing apparatus thereof of water oxygen permeability.
Background technology
All be subjected to the erosion of water oxygen easily at the article in multiple fields such as food, photoelectric device, shorten serviceable life or do not reach practical requirement at all.Whether can reach the requirement in this field for various substrates, various encapsulated layer, just need to measure their water oxygen permeability.US 2002/0152800A1 (open day is on Dec 24th, 2002) discloses the corresponding enclosed chip package metals calcium to be measured of a kind of usefulness, calculates the water oxygen permeability of enclosed chip by the variation of CCD imaging method judgement Ca layer gray scale and thickness.Thereby the variation of the gray scale of the image by taking Ca compares with the thickness curve of the gray scale-Ca of the standard that performs in advance and determines the thickness of present Ca layer, convert out water oxygen permeability again, step is various, and the one side of its substrate will be as under the environment that seals, the requirement height of method and apparatus.
Summary of the invention
For solving the problems of the technologies described above, the invention provides the method for testing and the testing apparatus thereof of the water oxygen permeability that a kind of method of testing is simple, equipment requirements is low.
The method of testing of water oxygen permeability of the present invention may further comprise the steps:
(1) preparation of sample
(1) in side evaporation one deck reactive metal layer of substrate layer, thickness is 30nm-500nm;
(2) with encapsulated layer the reactive metal layer on the substrate layer is carried out corresponding encapsulation;
(3) select the process that another kind of substrate layer or another kind of encapsulated layer repeat (1) (2), make a sample again;
The two-layer water oxygen permeability that above-mentioned three kinds of layers satisfy wherein is known, and sample is transparent at least simultaneously;
(2) measurement of sample surfaces reflectivity
The optical reflectivity of measuring its metal level on corresponding optical system simultaneously over time;
(3) estimation of encapsulated layer water oxygen permeability
The rate of change of the reflectivity of reactive metal layer has following relation
B=dR/dt ∝ (V Substrate layer+ V Encapsulated layer) (1)
Wherein R is a reflectivity, and t is the time, V Substrate layerBe the water oxygen permeability of substrate layer, V Encapsulated layerWater oxygen permeability for encapsulated layer.
Therefore the reflectivity that obtains two samples can be expressed as follows over time
B a=dR/dt∝(V 1+V 2) (2)
B b=dR/dt∝(V 1+V 3) (3)
V wherein 1Be the water oxygen permeability of substrate layer or encapsulated layer, V 2Be the water oxygen permeability of encapsulated layer or substrate layer, V 3Be the substrate layer to be measured or the water oxygen permeability of encapsulated layer, V 1And V 2Numerical value known, (2) formula and (3) formula are divided by and are obtained V 3
Reactive metal layer can be calcium, barium, sodium, lithium.
The testing apparatus of water oxygen permeability of the present invention comprises as lower member: light source, polaroid, part light-reflecting sheet, three photodetectors, data acquisition system (DAS), computing machine, 1/2nd beam splitting chips; Be fixed as the light of vertical polarization behind the light process polaroid (2) that light source (1) sends, a part reflexes to photodetector (5) light for referencial use through glass lithography sheet (4), remaining light is divided into aplanatic two-beam branch by beam splitting chip (7) and is clipped on the sample, reflected light through sample is detected device (9) and (10) reception, and lock-in amplifier (11) is passed through simultaneously by computing machine (12) record in detector (5), (9), (10).
Light source can be the known laser instrument of wavelength.
Data acquisition system (DAS) can be lock-in amplifier or data collecting card.
Testing apparatus can also comprise the chamber of placing sample, can charge into air, oxygen, water or steam according to different test environment requirements in the chamber, charges into the infiltration that oxygen, water or steam can be accelerated water oxygen, shortens the test duration.
The invention has the beneficial effects as follows: when the thinner thickness of reactive metal layer, its reflectivity is directly relevant with metal thickness, directly measures the permeability that the mode that encapsulates the active metal surface reflectivity obtains water oxygen constantly in difference thereby can adopt, and method is simple.Adopt measure simultaneously two simultaneously the encapsulated layer of the active metals of preparation reflectivity over time, a side of substrate that does not just need sample is under sealed environment, equipment requirements is low.
Description of drawings
Fig. 1 is the testing apparatus of water oxygen permeability of the present invention;
Fig. 2 A for structure among the embodiment 1 is: the reflectivity time diagram of the sample of the laminated film encapsulated layer of glass substrate/Ca (30nm)/organic-inorganic alternate multiple and thick film thereof;
Fig. 2 B for embodiment 1 structure is: the reflectivity time diagram of the laminated film encapsulated layer of pet substrate/Ca (30nm)/organic-inorganic alternate multiple and thick film thereof;
Fig. 3 A for structure among the embodiment 2 is: the reflectivity time diagram of the sample of the laminated film encapsulated layer of glass substrate/Ca (100nm)/organic-inorganic alternate multiple and thick film thereof;
Fig. 3 B for structure among the embodiment 2 is: the reflectivity time diagram of the sample of the laminated film encapsulated layer of PET-ITO substrate/Ca (100nm)/organic-inorganic alternate multiple and thick film thereof;
Fig. 4 A for structure among the embodiment 3 is: the reflectivity time diagram of the sample of the laminated film encapsulated layer of glass substrate/Ca (500nm)/organic-inorganic alternate multiple and thick film thereof;
Fig. 4 B for structure among the embodiment 3 is: the reflectivity time diagram of the sample of the laminated film encapsulated layer of PET-TiN/UV matrix plate/Ca (500nm)/organic-inorganic alternate multiple and thick film thereof.
Embodiment
Embodiment 1: to the measurement of the water oxygen permeability of the laminated film of organic-inorganic alternate multiple and thick film thereof
The first step uses the laminated film of organic-inorganic alternate multiple and thick film thereof that the calcium layer is encapsulated
The washing agent of (1) utilization heat is ultrasonic to be cleaned clear glass and pet substrate with the ultrasonic method of deionized water, places it in oven dry under the infrared lamp after the cleaning, and the water oxygen permeability of pet substrate is known.
(2) preparation of calcium metal layer: above-mentioned cleaning, drying glass substrate and pet substrate are placed in the vacuum chamber, be evacuated to 1 * 10 -3Pa, evaporation layer of metal calcium on aforesaid substrate then, the evaporation speed of material film is 3nm/s, thickness is 30nm.
(3) preparation there is calcium layer glass substrate and pet substrate compound packaging film, has calcium layer glass substrate and pet substrate to place vacuum coating equipment preparation, be evacuated to 4 * 10 with organic-inorganic alternate multiple and thick film thereof -4Pa.The UV of evaporation one deck liquid state solidifies glue (UV STRCTL 352, Le Tai company) on the calcium layer, and making its curing, irradiation time with the ultraviolet ray irradiation is 5min, and UV solidifies glue and becomes smooth solid film through ultraviolet ray irradiation in-situ polymerization, and thickness is 300nm.At background pressure is 10 -4~10 -3Aerating oxygen under the Pa condition, the air pressure of regulating vacuum chamber is 0.40Pa, adopts the rafifinal target solidifying sputter on the glue to UV under the DC power of 96W, and substrate temperature is controlled at below 40 ℃, and growth time is 10min, and the aluminum oxide film thickness is 50nm.Repeat UV curing glue/aluminium oxide THIN COMPOSITE rete that above-mentioned steps prepares 2 cycles again.At last, feed inert nitrogen gas in glove box, the UV that adopts the knifing legal system to be equipped with one deck liquid state on above-mentioned thin layer solidifies glue, and 5min makes its polymerization with the ultraviolet ray irradiation, and thickness is 70 μ m.
Second step measured over time to the reflectivity of packaged calcium layer.It is that the laser of 633nm is through being fixed as the light of vertical polarization behind the polaroid 2 that He-Ne laser instrument 1 sends wavelength, a part reflexes to detector 5 light for referencial use through glass sheet 4, remaining light is divided into aplanatic two-beam branch by beam splitting chip 7 and is clipped on the sample 6 and 8 in the chamber 13,14 of placing sample, is detected device 9 and 10 through the reflected light of sample 6 and 8 and receives.Detector 5,9,10 pass through lock-in amplifier simultaneously by computing machine 12 records, and wherein detector 9 is the relative reflectance of sample 8 with the ratio of detector 5 acquired signal, and detector 10 is the relative reflectance of sample 6 with the ratio of detector 5 acquired signal.
Measurement result as shown in Figure 2.
Wherein sample shown in Fig. 2 A is that structure is: the laminated film encapsulated layer of glass substrate/Ca (30nm)/organic-inorganic alternate multiple and thick film thereof; Sample shown in Fig. 2 B is that structure is: the laminated film encapsulated layer of pet substrate/Ca (30nm)/organic-inorganic alternate multiple and thick film thereof.
The 3rd step was carried out the water oxygen permeability of the laminated film encapsulated layer of analytical estimating organic-inorganic alternate multiple and thick film thereof to the result who obtains in said process.
Adopt the relation of R=A+Bt to remove fitted figure 2A and B, the linear relationship that obtains as shown in FIG..Wherein R is a reflectivity, and t is the time, and B is a slope, is B=dR/dt.We can obtain (a) respectively (b) under two kinds of situations, B a=-3.23 * 10 -5, B b=-0.865
Can obtain by formula (1)
B a=dR/dt ∝ (V a+ V Encapsulated layer) (3)
B b=dR/dt ∝ (V b+ V Encapsulated layer) (4)
V wherein aBe the water oxygen permeability of glass substrate, V bWater oxygen permeability for PET.V aCompare V bCan think infinitely small, V bBe about 10g/m 2.day.
Be divided by by (3) (4) formula and just can calculate V Encapsulated layerBe about 3.8 * 10 -4G/m 2.day.
Embodiment 2: to the measurement of the water oxygen permeability of the laminated film behind the evaporation 150nmITO on the PET substrate
The first step uses the laminated film of organic-inorganic alternate multiple and thick film thereof that the calcium layer is encapsulated
The washing agent of (1) utilization heat is ultrasonic to be cleaned clear glass and PET-ITO composite base plate with the ultrasonic method of deionized water, places it in oven dry under the infrared lamp after the cleaning.
(2) preparation of calcium metal layer: shown in embodiment 1.
(3) encapsulate with embodiment 1 identical processing step and process conditions.
Second step measured over time to the reflectivity of packaged calcium layer.Film with above-mentioned packaged Ca is placed on the position 6,8 of Fig. 1 respectively, measures it over time.Measurement result as shown in Figure 3
Wherein sample shown in Fig. 3 A is that structure is: the laminated film encapsulated layer of glass substrate/Ca (100nm)/organic-inorganic alternate multiple and thick film thereof; Sample shown in Fig. 3 B is that structure is: the laminated film encapsulated layer of PET-ITO substrate/Ca (100nm)/organic-inorganic alternate multiple and thick film thereof.
The 3rd step was carried out the water oxygen permeability of analytical estimating PET-ITO composite base plate to the result who obtains in said process.
Adopt the relation of R=A+Bt to remove fitted figure 3A and B, the linear relationship that obtains as shown in FIG..Wherein R is a reflectivity, and t is the time, and B is a slope, is B=dR/dt.We can obtain (a) respectively (b) under two kinds of situations, B a=-4.46 * 10 -5, B b=-0.269,
Can obtain by formula (1)
B a=dR/dt ∝ (V a+ V Encapsulated layer) (3)
B b=dR/dt ∝ (V b+ V Encapsulated layer) (4)
V wherein aBe the water oxygen permeability of glass substrate, V bWater oxygen permeability for PET-ITO.V aCompare V bCan think infinitely small, wherein V Encapsulated layerEmbodiment 1 records 3.8 * 10 -4G/m 2.day.
Be divided by by (3) (4) formula and just can calculate V bBe about 0.229g/m 2.day.
Embodiment 3: to the measurement of the water oxygen permeability of the laminated film of the TiN/UV glue in 2 cycles of evaporation on the PET substrate
The first step uses the laminated film of organic-inorganic alternate multiple and thick film thereof that the calcium layer is encapsulated
The washing agent of (1) utilization heat is ultrasonic to be cleaned clear glass and PET-TiN/UV glue composite base plate with the ultrasonic method of deionized water, places it in oven dry under the infrared lamp after the cleaning.
(2) preparation of calcium metal layer: shown in embodiment 1.
(3) the compound packaging film of organic-inorganic alternate multiple and thick film thereof is with embodiment 1.
Second step measured over time to the reflectivity of packaged calcium layer.Film with above-mentioned packaged Ca is placed on the position 6,8 of Fig. 1 respectively, measures it over time.Measurement result is illustrated in fig. 4 shown below.Wherein sample shown in Fig. 4 A is that structure is: the laminated film encapsulated layer of glass substrate/Ca (500nm)/organic-inorganic alternate multiple and thick film thereof; Sample shown in Fig. 4 B is that structure is: the laminated film encapsulated layer of PET-TiN/UV matrix plate/Ca (500nm)/organic-inorganic alternate multiple and thick film thereof.
The 3rd step was carried out the water oxygen permeability of analytical estimating PET-TiN/UV glue composite base plate to the result who obtains in said process.
Adopt the relation of R=A+Bt to remove fitted figure 4A and B, the linear relationship that obtains as shown in FIG..Wherein R is a reflectivity, and t is the time, and B is a slope, is B=dR/dt.We can obtain (a) respectively (b) under two kinds of situations, B a=-1.28 * 10 -5, B b=-9.68 * 10 -4,
Can obtain by formula (1)
B a=dR/dt ∝ (V a+ V Encapsulated layer) (3)
B b=dR/dt ∝ (V b+ V Encapsulated layer) (4)
V wherein aBe the water oxygen permeability of glass substrate, V bWater oxygen permeability for PET-TiN/UV glue.V aCompare V bCan think infinitely small, V Encapsulated layerEmbodiment 1 is measured as 3.8 * 10 -4G/m 2.day.
Be divided by by (3) (4) formula and just can calculate V bBe about 2.87 * 10 -2G/m 2.day.

Claims (6)

1, a kind of method of testing of water oxygen permeability, measurement may further comprise the steps:
(1) preparation of sample
(1) side at substrate layer prepares one deck reactive metal layer, and thickness is 30nm-500nm;
(2) with encapsulated layer the reactive metal layer on the substrate layer is carried out corresponding encapsulation;
(3) select another kind of substrate layer or another kind of encapsulated layer to repeat the process of (1) (2), make a sample again;
The two-layer water oxygen permeability that above-mentioned three kinds of layers satisfy wherein is known, and sample is transparent at least simultaneously;
(2) measurement of sample surfaces reflectivity
The optical reflectivity of measuring its metal level on corresponding optical system simultaneously over time;
(3) estimation of encapsulated layer water oxygen permeability
The rate of change of the reflectivity of calcium layer has following relation
B=dR/dt ∝ (V Substrate layer+ V Encapsulated layer) (1)
Wherein R is a reflectivity, and t is the time, V Substrate layerBe the water oxygen permeability of substrate layer, V Encapsulated layerWater oxygen permeability for encapsulated layer;
Therefore the reflectivity that obtains two samples can be expressed as follows over time
B a=dR/dt∝(V 1+V 2) (2)
B b=dR/dt∝(V 1+V 3) (3)
V wherein 1Be the water oxygen permeability of substrate layer or encapsulated layer, V 2Be the water oxygen permeability of encapsulated layer or substrate layer, V 3Be the substrate layer to be measured or the water oxygen permeability of encapsulated layer, V 1And V 2Numerical value known, (2) formula and (3) formula are divided by and are obtained V 3
2. according to the described method of testing of claim 1, it is characterized in that described reactive metal layer is a calcium, barium, sodium, lithium.
3, a kind of testing apparatus that realizes the method for testing of the described water oxygen permeability of claim 1, this equipment comprises as the lower part: light source, polaroid, flat glass film, three photodetectors, data acquisition system (DAS), computing machine, 1/2nd beam splitting chips; Be fixed as the light of vertical polarization behind the light process polaroid (2) that light source (1) sends, a part reflexes to photodetector (5) light for referencial use through glass lithography sheet (4), remaining light is divided into aplanatic two-beam branch by beam splitting chip (7) and is clipped on the sample, reflected light through sample is detected device (9) and (10) reception, and data acquisition system (DAS) (11) is passed through simultaneously by computing machine (12) record in detector (5), (9), (10).
4, equipment according to claim 3 is characterized in that described light source is the known laser instrument of wavelength.
5, equipment according to claim 3 is characterized in that described data acquisition system (DAS) is lock-in amplifier or data collecting card.
6,, it is characterized in that described equipment also comprises the chamber of placing sample, charges into air, oxygen, water or steam in the chamber according to claim 3 or 4 or 5 described equipment.
CN 200510051425 2004-09-30 2005-03-04 Testing method for water oxygen permeability and its testing equipment Active CN100507510C (en)

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CN104596906A (en) * 2015-01-16 2015-05-06 上海大学 Water and oxygen air permeability measuring system with multiple measuring heads
CN104777084A (en) * 2015-03-23 2015-07-15 中山大学 Lock-in amplifier based gas transmission rate optical measurement method and system
CN106489071A (en) * 2014-07-09 2017-03-08 帕雷科技有限公司 Method for measuring the infiltration of the penetrant by film
WO2022267218A1 (en) * 2021-06-24 2022-12-29 华中科技大学 Permeability measurement apparatus and permeability measurement method

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JPH01307635A (en) * 1988-06-03 1989-12-12 Hamamatsu Photonics Kk Method of evaluating material transmission performance of thin film for testing
US4873430A (en) * 1988-10-25 1989-10-10 International Business Machines Corporation Method and apparatus for optically measuring characteristics of a thin film by directing a P-polarized beam through an integrating sphere at the brewster's angle of the film
US5282380A (en) * 1992-06-30 1994-02-01 Millipore Corporation Integrity test for membranes
EP1072880A1 (en) * 1999-06-21 2001-01-31 Georges H. Dr. Lyssy Process and device for measuring the water vapour permeability of a film or membrane
GB2370649B (en) * 2000-11-09 2003-06-25 Toppan Printing Co Ltd Measurement of rate of transmission of a vapour through a sample
KR100859818B1 (en) * 2001-03-29 2008-09-24 코닌클리케 필립스 일렉트로닉스 엔.브이. Method and apparatus for measuring the permeation rate of a substrate, method for testing a set of substrates from a batch on permeability, and method for measuring the permeation rate of an encapsulation
WO2003029786A1 (en) * 2001-10-03 2003-04-10 University Of Western Sydney Detection and measurement of oxygen permeation across a film
JP4151555B2 (en) * 2003-10-20 2008-09-17 東洋製罐株式会社 Method for producing containerized food

Cited By (6)

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CN106489071A (en) * 2014-07-09 2017-03-08 帕雷科技有限公司 Method for measuring the infiltration of the penetrant by film
CN106489071B (en) * 2014-07-09 2019-06-04 帕雷科技有限公司 For measuring the method for passing through the infiltration of penetrant of film
CN104596906A (en) * 2015-01-16 2015-05-06 上海大学 Water and oxygen air permeability measuring system with multiple measuring heads
CN104777084A (en) * 2015-03-23 2015-07-15 中山大学 Lock-in amplifier based gas transmission rate optical measurement method and system
CN104777084B (en) * 2015-03-23 2018-02-16 中山大学 A kind of gas permeation rate measuring method and system based on lock-in amplifier
WO2022267218A1 (en) * 2021-06-24 2022-12-29 华中科技大学 Permeability measurement apparatus and permeability measurement method

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