DE2434129A1 - MOISTURE SENSITIVE ELEMENT - Google Patents

Description

EIKENBERG & BRÜMMERSTEDT PATENT LAWYERS IN HANOVER

5okyo Shibaura Electric Co. Ltd. 235/85

Moisture sensitive element

The invention relates to a moisture sensitive Element, which has the corner, changes in the ambient humidity as changes in electrical resistance.

It is already a moisture sensitive element known, which is applied to an inorganic insulating substrate layer of fine powdery metal oxides such as

Contains Fe-zCL, Fe ₀ O-, Al ₀ CU and Cr ₀ CL. This element is based 3 4 23 23 23

on the excellent hygroscopicity that these metal oxides generally have. The layer of fine powdery metal oxides therefore speaks to changes in the environmental fire with noticeable changes in the electrical resistance stable. However, the layer made of the finely powdered metal oxides has a very high resistance, so that the element small changes in the ambient humidity not accurate enough can display electrically. In addition, the reproducibility

4 09885/1102

the measured values and the aging resistance are not satisfactory.

Furthermore, is a moisture-sensitive element known which one PiIn. made of metal oxides. This Element is small in size and light in weight. It also responds quickly to Peuchte changes and it works Over a wide temperature range ',' from low to high temperatures, quite satisfactory. However, it does the measurement of the efficiency rate is consistently not accurate enough, and besides, the sensitivity of this element is bad, because it is unstable and because the PiIm is not homogeneous enough is. Moreover, this element cannot be mass-produced.

In principle, pure moisture-sensitive elements can be used materials can also be used which can be summarized under the designation "mixed oxide semiconductors" and which are semiconductors made from various metal oxides. Oxide semiconductors have a lower resistance than all of them raw metal oxides, and one can therefore assume that their resistance depends on absorption and desorption changes greatly from moisture. Most semiconductors of this type, also called "thermistors" (i.e., thermally sensitive Resistors), however, have a large negative temperature coefficient of resistance, see above that their resistance changes significantly even with small changes in temperature. The use of these semiconductors for moisture Measurement is therefore not possible if, as is normally the case with the pail, a temperature change occurs during the measurement can.

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. Hit of the invention is now intended to be a moisture-sensitive Element based on an oxide mix semiconductor be created, which is very resistant to aging, has a high sensitivity, good reproducibility which shows measured values and has only a small temperature coefficient of resistance.

Surprisingly, it has been found that this goal can be achieved by a semiconductor which is according to the invention characterized by the composition

89.9 to 20.0 Mo I /. ZnO

0.1 to 20.0 MoljS Cr ₂ O ₅ and

10.0 to 60.0 mol $ of at least one third metal oxide,

this further metal oxide being selected from the group consisting of Li ₂ O, Ha ₂ O, E ₂ O, Rb ₂ O, Cu ₂ O, BaO, SrO, CaO, PbO, MnQ, MO, CoO, MgO, CdO, CuO, FeO , BeO, TiO ₂ , GeO ₂ , ZrO ₂ , MnO ₂ , TeO ₂ , SnO ₂ , SiO ₂ , CeO ₂ , ThO ₂ , HfO ₂ , Hb ₂ O ₅ , Ta ₃ O ₅ , Sb ₃ O ₅ , V ₃ O ₅ , WO ₅ , MoO ₅ and TeO ₅ .

Of course, the sum of all components always makes 100 M0I5S.

The third metal oxide can, as can be seen from the above list, be the oxide of a monovalent metal (Me ') or the oxide of a divalent metal (Ms), a tetravalent metal (Me), a pentavalent metal (Me) or a hexavalent metal (Me). The oxides may be more metals of the same rank in mixture with one another, and it can also oxides of metals

409885/1102

different ¥ ability together that Form "third metal oxide".

The invention and the gate parts achieved therewith are below with reference to the drawings and in exemplary embodiments explained in more detail. In the drawings show:

Pig. 1 graphically shows the dependence of the specific resistance on the content of CU for an element according to the invention

with a monovalent third metal oxide, the molar ratio of Me «O to ZnO is kept constant,

Pig. 2 graphically the dependency of the specific Resistance of the content of O- for an element according to the invention

with a divalent third metal oxide,

(2)

where the molar ratio of Me ^x '0 to

ZnO is held constant, Pig. 3 graphically the dependency of the specific

Resistance on the content of Cr ^ O for an inventive element having a third tetravalent metal oxide, wherein the molar ratio of Me 'is kept constant 0 "to ZnO ^,

Pig. A graphical representation of the dependence of the specific resistance on the content of Cr ₂ O for an element according to the invention

with a pentavalent third metal oxide, 409885/1102

where the molar ratio of Mei ^ 'O _c to ZnO is kept constant, and

Pig. 5 graphically shows the dependence of the specific resistance on the content of O, for an element according to the invention

with a hexavalent third metal oxide, • where the molar ratio of Me ^ 0, to ZnO is kept constant,

Fig. 6 schematically shows the top view of a

Moisture measuring device with a moisture-sensitive element according to Invention,

Fig. 7 graphically shows the dependence of the specific resistance on the relative Moisture for a well-known moisture-sensitive Element at constant temperature,

8 to 22 graphically show the dependence of the specific resistance on the humidity for various moisture sensitive elements according to the invention at constant Cemperature ^ and

Figures 23 through 37 graphically show the changes in resistivity with temperature for various moisture sensitive elements according to the invention at constant humidity.
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The invention is based on the surprising finding that an oxide semiconductor, which in itself would be classified as a thermistor, proves to be an excellent moisture-sensitive one Element with low resistance and a low temperature coefficient of resistance proves when he has the composition

89.9 to 20.0 moles # ZnO,

0.1 to 20.0 moles of Cr ₂ O- and

10.0 to 60.0 moles of at least one

third metal oxide

Has. A semiconductor composed in this way shows a strong change in its resistance when the ambient I light changes with only very little influence of the ambient temperature

The third metal oxide can be the oxide of a monovalent, divalent, tetravalent, pentavalent or hexavalent metal. In the case of a monovalent metal oxide (Me ^ 'O) it is selected from the group Li ₂ O, ITa ₂ O, K ₂ O, RbgO and Cu ₂ O, in the case of a divalent metal oxide (Me ^' O) it is selected from the group BaO, SrO, CaO, PbO, MnO, UiO, CoO, MgO, CdO, CuO, 3? eO and BeO, in the Ealle a tetravalent metal oxide (Me ^ 'O ₂ ) it is selected from the group EiO ₂ , GeOg , ZrO ₂ , 1InO ₂ , EeO ₂ , SnO ₂ , CeO ₂ , ThO ₂ and HfO ₂ , in the case of a pentavalent metal oxide (Me Oc) it is selected from the group Mb ₂ O, -, ^ ^a 2 ° 5j ^{st un} ^ ^ ^m ^ ^a ^ l ^{e it} hexavalent metal oxide (Me * O

and ^ 2 ^ 5 ^'un ^ ^ ^m ^ ^a ^ l ^{e it} hexavalent metal 3, finally, it is selected from the group ,, WO MoO * and TeO, Any desired combination of the above oxides can be used.

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The "preferred limits of the composition are

80.0 to 30.0 moles of ZnO, 5.0 to 20.0 moles of Cr ₂ O _5, and 15.0 to 50.0 moles of the third metal oxide.

A semiconductor that controls the composition has proven to be particularly good

60 mol $ ZnO,

10 mol / o Cr ₂ O ₃ and

30 mol # of the third metal oxide

owns.

As soon as the content of Cr ₂ O ₅ drops below 0.1 mol $, or as soon as the third metal oxide has a content of less than 10 mol $, an element results with a resistivity of more than 100 mils. Such an element is practically unsuitable as a moisture-sensitive element. The same applies when the content of ZnO is less than 20 mol % and / or when the content of the third metal oxide exceeds 60 MoVfo.

In Pig. 1 to 5 of the drawings, the change in specific resistance for various elements according to the invention is shown graphically as a function of the Cr ₂ O ₅ content. In all spheres, the ratio of the third metal oxide to ZnO is kept constant at 1: 3. In Fig. 1, the third metal oxide is a monovalent metal oxide,

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and accordingly are in the pig. 2 to 5 as the third metal oxide various oxides of bivalent, tetravalent, pentavalent or hexavalent metals are used as a basis. For the various euro trains in the Pig. 1 to 5 the following applies in detail:

Curve a : Me = Li Curve b: : Me ⁽ⁱ⁾ = K Curve C. : Mei ¹ > = Cu Curve a : Me ⁽² > = Sr Curve e • Me ⁽²⁾ = Ni Curve "Me ^ ² ) = Co Curve S. : Me ⁽⁴⁾ = Ti Curve : Me ⁽⁴⁾ = Sn

Curve i: Me ^ ' = Ce Curve D ': Me ⁽⁵⁾ = Ta Curve k: Me ^ ' = Sb Curve J_ · JXiO = Y Curve m: Me = W Curve n: Me ^ ⁶ ^ = Mon Curve o: Me ^ ⁶ ^ = Te

From Figs. 1 to 5, it is confirmed that the resistance of the semiconductor element whenever the content of CrpO ^ is greater than 20 MoIjS, rises to over 100 Milan, whereby the Element is unsuitable as a moisture-sensitive element. A further evaluation of these curves also shows that the upper Limit for the content of ZnO is 89.9 mol #.

To produce a moisture-sensitive element according to the invention, one of the pure oxides of the subject Metals are assumed, but it can also be assumed from corresponding amounts of a metal compound, which when heated passes into the oxides. Examples are the hydroxides, carbonates and the oxalates of the metals concerned.

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_ 9 -

The starting materials used are accurately weighed, thoroughly mixed in a ball mill and then at a relatively low temperature of, for example 600 to 90O ⁰ G presintered. The pre-sintered mass is then comminuted to a finely divided powder, which can also be done again in a ball mill. The powder is then mixed with a binder, for example with polyvinyl alcohol, and then shaped under a pressure of about 100 to 1000 kg / km into a shaped body, for example into a plate 10 mm wide, 20 mm long and 1 mm thick. The shaped body is then finally subjected to a main sintering at about 1000 to 1300 ^° C., the maximum temperature being maintained for about 1 to 5 hours. This main sintering can take place in air.

One using an element of the invention The humidity measuring device produced is shown in FIG. 6. The reference numeral 1 denotes that which is sensitive to moisture Element, while the reference numerals 2 and 3 indicate two electrodes made of a material that adheres well to the element 1 adheres and also has only a very low contact resistance to element 1 »The material can have a high temperature be baked-on silver color.

It has already been mentioned that the moisture-sensitive element according to the invention hardly changes its resistance with temperature, which is surprising and could not have been foreseen in view of the fact that the element according to the invention belongs to the group of oxide semiconductors. Furthermore, the element according to the invention also has excellent aging _{resistance 9} by increasing its resistance

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- ίο -

even "changes only to a negligibly small extent when used over very long periods of time. In addition, it responds to changes in humidity much more quickly than the known elements fo, and about 2 seconds for humidity changes of ί 20 S &. In the known elements, on the other hand, the response speed for humidity changes from 0 to 100 5 ^ is 40 seconds and for humidity changes of - 20 % is 5-7 seconds Furthermore, with the element according to the invention there is no (or at most only a very slight) difference in the measured values when the resistance is measured on the one hand with decreasing humidity and on the other hand with increasing humidity can be economically mass-produced and the starting materials are available cheaply en.

It is not yet entirely clear why the inventive Element has the excellent properties outlined above. Perhaps one can assume that with one When the surface of the element is covered with water vapor, the element becomes electrically conductive in the same way as (what known) a semiconductor when it absorbs a gas.

Numerical examples are given below the invention explained in more detail. Some of the results found are summarized in Tables 1 to 6 attached and partly also shown graphically in FIGS. 8 to 37. FIG. 7 is related to this

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Figures and "refers to a" known moisture sensitive Element.

A total of 194 specimens were produced, the to composition in the field

90 to 18 mol # ZnO _s

0 to 22 moles $ Gr ₂ O, and

10 to 62 mol $ of third metal oxides.

Of these samples, 174 had a composition within the scope of the invention (hereinafter referred to as "Examples"), while 20 Prohen had a composition outside the scope of the invention (hereinafter referred to as "reference sample").

In all cases, the Dahei exactly balanced starting materials (in the specified amounts in the tables respectively) are intimately mixed in a ball mill together and presintered long for one hour hei 800 ⁰ C. The pre-sintered mass was then comminuted to a finely divided powder, to which polyvinyl alcohol was added as a binder. The mixture thus obtained was then pressed into sheets 10 mm wide, 20 mm long and 1 mm thick. These plates were then subjected to the main sintering for two hours at 1000 kg / cm ^{2 in an electric furnace maintained at 1100 to 1300 ° C..}

To produce a humidity measuring device, conventional silver electrodes were baked onto the plates, with either elemental Ag or Ag ₂ O being used as the starting material for these electrodes. Since the sintered material is temperature stable, the caking of the electrodes within a

409885/1 1 02

wide temperature range of, for example, 400 to 800 ⁰ C take place.

For each sample, the resistance was ^{measured at 25 °} C. and a relative humidity of 0 $ (Rp, - (O $ RH)), as well as the ratio of R ₂₅ (0 $ RH) to R ₂₅ (100 $ RH), ie the ratio of the resistances at 0 $ relative humidity and 100 $ relative humidity, in each case for a temperature of 25 ⁰ C.

The measurement results are set out in Tables 1 to 6, together with the composition of the respective samples. Table 1 relates to samples which contain the oxide of a monovalent metal as the third metal oxide, while Tables 2 to 5 relate to samples in which the third metal oxide is divalent, tetravalent, pentavalent or hexavalent. Finally, Table 6 shows the results for samples in which mixtures of Mei '0, Me ^' 0, Me ^ 'O ₉ , MeA ^ Oj- and Me ^' 0 were used as the third metal oxide.

Some of the aforementioned samples were tested for changes in resistance with relative humidity tested, in each case at a constant temperature of 25 C. The results obtained in this investigation are shown graphically in FIGS. 8 to 22, the figures (in the order) relating to Examples 6, 13, 23, 57, 60, 78, 90, 100, 113, 117, 126, 135, 139 and I46.

For comparison, the resistance / humidity curve was also recorded for a known moisture-sensitive element, namely for an element that consisted of a sintered mixture of silicon with a metal oxide. The for it

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The results obtained are shown in FIG. 7. It can be seen in particular from FIG. 7 that considerable differences in the measured values occur depending on whether the measurements are increasing with Humidity or with decreasing humidity. The direction of the measurements is indicated by a small one Arrow indicated in the relevant curve. In FIGS. 8 to 22, too, the measurements were in each case with increasing and carried out with decreasing humidity (see also the arrows there) but no or only slight. Differences in the measured values occurred. The measured values are therefore very much better reproducible with the elements according to the invention than with the known element.

Finally, the change in resistance with temperature was also measured for some samples, in each case at relative humidities of 0 fo and 100 fo. The results in this regard are illustrated in FIGS. 23 to 37, these figures relating (in order) to Examples 3, 15, 25, 39, '50, 66, 74, 91, 102, 111, 116, 126, 132 , 137 and 147. The curves valid for a relative humidity of 0 ^c ß> are shown in solid lines and labeled "0 5 $ RH", while the corresponding curves for 100 $ relative humidity are shown in dashed lines and labeled "100 $ RH". From the figures 23 to 37 can be clearly seen that the moisture-sensitive element of the invention, although it has in accordance with a composition as osidic semiconductor, its resistance in the temperature range of 0 to 100 ⁰ O changed only very slightly

40988B / 1102

- H

TABLE 1

1 ZnO
(mol%) Cr ₂ O
(mol 3
%) «Β« ¹ »
(mol O
%) 10 I. ■ 1 I. Il ^R 25
m ^m R ₂₅ (0% RH) relation 2 90 0 Μβ ⁽¹ » = Li Ii Il Il 155 R ₂₅ (100% RH) It 1 Il Il Ii = Well Il 3 170 175 example 2 89.9 0. 1 ι: = Li Il Il 74 190 • »ι 3 ir ! I 11 = Well Il 63 785 Il 4th ■ ι Il :; = κ K Il 57 810 Ii 5 ■ ι ; ι ΐ! = Rb ti Il 61 745 Il 6th Il Il II = Cu 15th 30th 78 830 ι: 7th 80 5. 0 ! I = Li Il 11 20th 710 ι: 8th Il Il » = Well 13th 1640 κ 9 ■ ι 71 I! = K 17th 1855 ΐι ιό Il H I = = Rb 11 1705 11 Il Il II = Cu 24 2080 Il 80 5. 0 K = Well 10 1570 (I. = K 2120 ; ι = Rb Il = Cu 12th :) = Li Il 13th 60 10 η -Li 0.50 η 14th Il Il Il = Well 0.26 8090 π 15th π Il « = K 0.34 10770 η 16 η Il ι: = Rb 0.47 9565 ■ ι Il Il ι; = Cu 0.63 9135 7940 '

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j
example 17th 60 10 Ke (D = Li 10 0.38 83 9675 :; = Well " 87 U = K " 65 il 18th Il Il 'Il = K ^l! 0.42 69 9310 5) = Rb " = Cu " II 19th 30th 20th Il = Li 50 28 62 1605 It 20th Il Il Il = Well " 34 1410 ι: 21 Il Il i) = K " 40 156 1300 ι; 22nd Il Il t: = Rb " 46 215 1175 j ι « 23 Il Il · ■ ' = Cu " 22nd 1685 Il 24 I! Il / JI = Li 10 20th 1720 ΪΙ = Well " I! = K " Γ = Rb " = Cu " Il 25 ' 20th Il I; = Li 60 70 845 " 26th Il η Il = Well " 78 810 I. Ii 27 20th 20th It = K 60 760 Il 28 Il Il Il = Rb " 720 Il 29 Il Il II- = Cu " 905 Il 30th Il Il *
\ Il = Li 30 885 \ \ ■ 1 = K " Il 31 Il ti Il = Pb " 920 \ Il = Cu " Be ziog 3 18th 20th Il = K 62 180 ti 4th Il 22nd Il = Cu 60 145

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TABLE 2

5 33 ZnO Cr O Me ⁽²⁾ 0 = Approx 10 _R. R ₂₅ (0% RH) 6th 34 (mol%) 2 3 (] = Ba Il (0% RH) R_ _t . (100% RH)
ZD Example32 35 (mol%) = Sr Il (ΜΩ) relation Il 36 90 0 TlOl%) = Approx Il 200 185 Cl 37 11 Il = Pb Il 150 190 ι: 38 89.9 0.1 Me * ²⁾ = Ba = Mn It 75 545 H 39 Il Il W. = Ni Il 82 590 Jl 40 Il Il Ii = Co Il 66 640 ■ I 41 Il Il II = Mg Il 87 735 Il 42 Il Il '■ = Cd Il 73 560 Il 43 II ti '· = Cu Il 61 705 It 44 Il It Il = Fe ■ 1 58 680; It Il Il It = Be It 60 770 j Il ■ I Il ti = Ba ■ 1 69 710 11 η Il Il 15.0 74 665 11 It Il 77 635 ti Il It 85 520 80 5.0 « 31 1435 Il Il

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Example 45

45 80 46 Il 47 Il 48 Il 49 Il 50 Il 51 Il 52 60 53 Il 54 It 55 Il 56 Il 57 Il 58 II

5.0

10

Me ^{2) = Cal5.0 Il 28 1620 i Il = Pb Il 12th 1915 Il = Ni Il 22nd 1535 Il = Co Il 17th 1820 SI = Mg Il 26th 1580 II = Fe 3 35 1325 ί " = Sr II 14th 1870 Γ = Mn Il ! I = Co (I. II = Ni Il V = Be 30th Il = Approx Il 0.65 6730 Il = Pb Il 0.51 9315 11 = Cd Il 0.74 6040 Il = Cu Il 0.86 7225 Il = Co 10 0.97 5655 ί " = Ba Il 0.48 9635 Γ = Sr Il U = Approx It Γ = Pb Il 0.58 8710 ■ = Cu II ■ = Co

4098 85/1 1Ü2

example 59 30th 20th 20th Ke < ^! ^ = Approx 50 37 1075 Il 60 ■ ι II tr Il = Co Il 40 1020 Il 61 II Il Il Il = Fe Il 28 1320 IS 62 Il Il Il Il = Cu Il 32 1145 Il 63 Il 11 ■ ι Il = Ba 5 23 1400 il Il = Sr Il • 1 = Approx Il j · «
} = Pb 5 V = Mn Il (
". Il
I.
Ι « = Ni Il
II 1
I.
i Il
I. -LO
= Fe Il 20th f
/ Il
r
ι = Cu Il 22nd V ¹ = Cd U It 64 20th Il = Sr 60 75 735 Il 65 Il Il = Fe Il 83 655 Il 66 II Il = Ni Il 90 560 η 67 Il Il = Be Il 71 770 - 68 ir ■ 1 = Ba Il 67 805 « 69 Il Γ " = Approx 10 70 795 Il -Pb ■ 1 1" = Mn I. = Ni Il I " = Co Il i " = Fe Il relation 7th 18th Il = Cd 62 170 160 If 8th Il Il = Mg 60 240 125

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TABLE 3

9 ZnO Cr O Me ¹ V = Ge 10 .0 ^R 25 R ₂₅ (0% RH) 10 90 / j
(mol%) C.
(xnol%) = Ti ι: (0% RH)
(ΜΩ) R ₂₅ (100% RH) relation 70 Il 0 Me ^ = Ti = Ge Il 180 180 Il 71 89.9 Il = Zr Ii 145 195 Example. 72 Il 0.1 · ■ = Mn I! 72 610 Il 73 11 ■ 1 9 = Te Il 86 575 Ιΐ 74 II Il If = Sn Il 61 790 ι: 75 ti Il . · -Si Il 74 605 ϊι 76 Il Il Il = Ce Il 69 590 Ii 77 11 Il <t = Th Il 57 860 Il 78 11 Il ;. “Hf Ii 50 825 I. 79 11 Ii Il = Ge Il 65 780 Il 80 If II Il = Zr 15th 73 595 ·· 81 80 Il η = Mn » 79 535 If 82 Il 5.0 Il = Te Il 28 1630 Il 83 Il Il Il = Si r. 33 1445 V 84 Il Il Il = Ce Il 12th 2070 Il 85 Il ι: Il ! I 19th 1910 H Il Il (I. 21 1765 H Il Il 37 1320

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example 86 94 80 5.0 Met ¹
ί = Ge 3.0 16 1880 95 1 u
I. = Zr Ii 96 1
' Il
S. = Mn Il 97 ! » = Te Il L. = Zr Il ü 87 60 10 II = Ge 30th 0.39 10410 dd 88 60 10 (I. = Te 30th 0.45 8955 89 II Il Il = rin Il 0.52 8060 11 90 : i Il t: = Ce 1" 0.66 7120 Il 91 11 If ι; = Ti 11 0.74 6535 Il 92 ti It f " = Ge 10 0.61 7685 U. < u '
1 = Zr Il ι » = Ce Il Il 93 It I! / '«
) = Hf
ml- » ι: 0.77 6390 ■ \: - ± 11
= Mn Il
Il :. 30th 20th : ι = Te 50 26th 1610 Il II Il ; t == Sn 33 1325 Il If Il j; = Si U 39 1285 ! I ft ι: ;: ι; 44 1170

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example 98 20th 20th , Me ^ I. ■ = Ti 5 21 1740 Il Ii = Ge Il ! · ι; II = Zr Il Ϊ7 Il Il = Mn Il Il / π = Te Il 20th Il = Sn Il Il Il = Si Il Il = Ce Il ι- = Th Il K- = Hf '■ 11 99 fl H = Ti 60 71 765 Il 100 π Il = Zr Il ■ 84 710 !1 101 18th Il It = Te Il 87 670 II 102 Il ; ι π = Sn Il 69 785 Il 103 » Il = Si Il 60 820 It 104 20th η = Hf 60 55 940 Il 105 ti (" = Ge 10 62 805 = Zr Il ii = Mn Il = Te Il = Ce Il , = Sn Il relation 11 20th = Si 62 165 185 ■ I 12th 22nd = Sn 60 220 130

409885/1 102

TABLE k

13th ZnO ^Cr 2 ° 3 M. , ' 2 , 1Sl ^R 25 55 R ₂₅ (0% RH) 14th JXiOL-S) / τη / - <1 S ^ 1 ( TO / ^ 68 R_ _c (100% RH) 106 V IH (J J- ¹ B j j \ IHC = Nb 10 (0% RH) 76 Be 2HJg 107 90 0 Me (5) = Ta ^i! (ΜΩ) 91 175 Il 108 ■ 1 If Il = Nb " 200 72 185 example 109 89.9 0.1 Ii = Ta " 165 580 Il 110 Il II Il = Sb " 84 69 635 Il 111 If IJ Il = V " 76 720 I. 112 IE II Il = Nb 15.C 69 615 Il 113 80 5.0 K = Ta " 77 1720 Il 114 Il Il ! I = Sb " ι 24 1560 Il ■ i Il fl = v " 31 1395 ti Il Il Il = Nb 6.0 15th 2035 Il i: 1! j : i = Ta 3.0 12th 177Q 115 1
/ It = Sb " . 17th 116 \
I. η = V " 117 Ϊ
I.
\
\ ti = Nb 30 Il 118 60 10 Il = Ta ^I! 8340 π 119 Il Il Il = Sb " 0. 8125 11- Ii Il = v " 0. 7490 ■ 1 120 Il Il ■ 1 = Nb 15 0. 6660 ■ I 121 π ti II = Sb " 0. 7715 122 Il = Ta "
= V " 0. Il 123 1" Il Il
11 = Nb 50 8040 Il 124 30th 20th Il = Ta " 0. 1680 ir η Il ; t = Sb " 24 1520 Il Il Il Il = v " 36 1830 Il II It Il 19th 1465 38

A09885 / 1102

example 125 20th 20th It Il '= Nb 60 67 775 ti 126 Il Il Il Il = Ta Il 72 720 Il 127 Il Il Il It = Sb Il 55 885 Il 128 ti Il (" It = V Il 61 710 Il 129 It > ' / · ■ = Nb 15th 59 850 η \ = Ta It = Sb Il = V It relation 15th 18th 20th = Sb 62 155 150 Il 16 11 22nd = V 60 201 145

TABEIIE 5

17th ZnO
(mol Cr ₂ O
(mol 3
%) Me ⁽⁶⁾
(mol = w 10 ^R 25
(0% RH)
(Mfi) 68 R ₂₅ (0% RH) Needed 18th 90 0 Me ⁽⁶ > = Mon Il 150 62 R ₂₅ (100% RH) Il 130 11 Il Il = W I! 165 21 165 example 131 89.9 0 .1 ti = Mon 10 71 18th 180 Il 132 89.9 0 .1 Il = Te Il 16 775 Il 133 It Il Il = W 15th 820 Il 134 I: 5 .0 ■ i = Mon Il 885 ·· 135 Il M. Il = Te Il 1620 Il Il t: ρ 1815 1930 "

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Example 13 6 137 89.9 5.0 1 "
/ Il = w 5 14th 2020 138 I. Il = Mon Il 139 Il = Te ir ι; 140 60 10 f Il
{ = w 30th 0.45 8775 Il Il Il 1 it = MO Il 0.32 9610 H 141 Il Il (" = Te 11 0.21 10330 11 Il t! I- = w 15th 0.30 9701 142 11 = Mon 11 Il 143 Il Il Il = Mon Ii 0.26 9910 144 i! = Te Il Il 145 30th 20th ί " = W 50 24 1425 I? K 11 {■■ = Mon 11 36 1305 11 Il Il {" = Te Il 39 1230 Il 146 ti Il Il = W 20th 21 1500 147 Il = Mon Il 148 11 = Te 10 It 19th 20th 20th ■ I = W 60 72 835 Il 20th ■ I » Il = Mon 31 88 720 II Il Il = Te It 69 980 relation 18th 20th = W 62 130 200 Il Il 22nd = Te 60 145 185

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TABLE 6

ZnO Cr O Third ^R 25 R ₂₅ (0% RH) Example 149 (mol Metal oxide
(molfo) (ΜΩ) R ₂₅ (100% RH) 60 10 / Me ⁽¹ ^ = Li 15 0.56 8950 150 lMe ⁽²⁾ = Mg " Il Il jMe ⁽¹⁾ = K - 0.75 9234 151 (Me ^ = Zr " Il ti (Me ⁽¹⁾ = Na " 0.38 11095 152 U ⁽⁵⁾ = v " Il ■ I , 'Me ⁽¹⁾ = Li " 0.43 9020 153 U ⁽⁶⁾ = Te " 154 Il I! [Me ⁽²⁾ = Co " 0.82 6305 Il Il (Me ⁽²⁾ = Ba " 0.51 9013 155 (Me ⁽⁵⁾ = Nb " Il Ii JMe ⁽²⁾ = Sr " 0.35 9500 156 U ⁽⁶⁾ = Te » 157 Il Il j Me 0.68 7750 Il Il | Me ⁽⁴⁾ = Ti 0.52 8028 158 Me ⁽⁶ U » Il ι: | ife ⁽⁵⁾ = V -
JMe ⁽⁶⁾ = Mo " 0.65 7520

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; piel 159 60 »F . 16c Il Il 161 "1 ; · 162 Il Il 163 Il Il 164 Il Il 165 Il ! I 166 η Ii 167 Il

/ • Me
^ Me (D
(2) = Li
= Pb 10
Il {here W. = Ti Il ■ 'Me U) = K Il {Me
1 (2) = Approx I! ^ Me (5) = Nb Ii ('Me
i (1) = Well 10 ]
^s ₍ Me (2) = Cd ti I.
! Me (6) = W If . '' Me (D = Cu ti -; Me
I. (4) = Zr II ! Me (5) = Ta Il tie
\ (D = Rb It Ina (2) = Mn El iMe ( ² O = Te H / Me (D = Li U / Me (5) = Nb Il [Me (6) = Mon » , 'Me (2) = Co It j Me (4) = Zr ■ 1 C Me (5) = Ta II / Me (2) = Ba ir iMe (*) = Ti Il • Me (6) = W Il Me (2) = Sr Il

= Te "

0.59

0.50

0.48

0.53

0.43

0.50

0.73

0.55

0.53

8210

7845

10095

8895

9427

9113

7520

7940

8140

409885/1 102

60 10 ■ ■ 1 27 - 0.49 2434129 Example 168 < _Me ^{(i |)} = Ti " 8098 Il If Me ⁽⁵⁾ = Ta "
. · (6) n ti 0.62 169 sMe = Mo
'Me ⁽³ ^ = Li 10 7875 Il ! Me ⁽²⁾ = Ba " Me ⁽⁴⁾ = Ti 5 Il η (Me ^ = V " 0.57 ¹
ι »170 Il Me ' ¹ ^ = Cu 10 8541 Me ⁽²⁾ = Sr ^I! ^ (4)
He ^VH '= Zr 5 ■ Il Ma ⁽⁶⁾ = Te ^1! 0.41 ¹¹ '171 Il 'Me ⁽¹ ^ = Na 10 10280 Me ⁽² ^ = Ca " _Me (5) _{= Ta 5} Il Me ⁽⁶⁾ = W » 0.53 - ¹¹ 172 'Me ⁽¹⁾ = K 10
Mrs "M" -i " 8609 we - Mn
Me ^vj; = Nb 5 Il , Me ⁽⁶⁾ = Mo " 0.69 173 Me ⁽¹⁾ = Li 10 7840 Me ⁽²¹ ^ Zr " Me ⁽⁵⁾ = V 5 Il Ue ⁽⁶⁾ = W " 0.74 174 ( Me ⁽¹ ^ = Na 10 9860 lMe ^(2} = Ba 5 i lie ⁽ ^ = Ti ^{! 1}
| ne ⁽⁵ ^ Sb -
[Me ⁽⁶⁾ = Te »

409885/1 102

Claims (8)

243-129 claims 1. Moisture-sensitive element made of an oxide semiconductor, characterized by the composition 89.9 to 20.0 MoI ^ ZnO, 0.1 to 20.0 M0I5S Or ₂ O ₃ and 10.0 to 60.0 moles of at least one third metal oxide, which is selected from the group Ii ₂ O, Na ₂ O, EpO, Rb ₂ O, BaO, SrO, CaO, PbO, MnO, NiO, CoO, MgO, CdO, PeO, BeO, CuO, GeO ₂ , ZrO ₂ , MnO ₂ , CeO ₂ , SnO ₂ , SiO ₂ , CeO ₂ ,! EhO ₂ , HfO ₂ , Hb ₂ Oc, Ta ₂ O ₅ , Sb ₂ O ₅ , V ₂ O ₅ , WO ₅ , MoO ₅ and IeO ₅ . 2. Moisture-sensitive element according to claim 1, characterized in that the third metal oxide is the oxide of a monovalent metal and is selected from the group Ii ₂ O, Na ₂ O, EgO, Rb ₂ O, Cu ₂ O or mixtures of these oxides. 3. Moisture-sensitive element according to claim 1, characterized in that the third metal oxide is the oxide of a divalent metal and is selected from the group BaO, SrO, CaO, PbO, MnO, NiO, CoO, MgO, CdO, CuO, FeO, BeO or Mixtures of these oxides is selected. 4. Moisture-sensitive element according to claim 1, characterized in that the third metal oxide is the oxide of a tetravalent metal and from the group IiO ₂ , GeO ₂ , ZrO ₂ , MnO ₂ , TeO ₂ , SnO ₂ , SiO ₂ , CeO ₂ , ThO ₂ , HfO ₂ or mixtures of these oxides is selected, 409885/1102 5. Moisture-sensitive element according to claim 1, characterized in that the third metal oxide is the oxide of a pentavalent metal and is selected from the group ITb ₂ Oe, Ia ₂ O, -, ShJO ^, T ₂ Oc or mixtures of these oxides. 6. Moisture-sensitive element according to claim 1, characterized in that the third metal oxide is the oxide of a hexavalent metal and is selected from the group ¥ 0 ,, MoO ₂ , IeO ~ or mixtures of these oxides. 7. Moisture-sensitive element according to claim 1, characterized by . the composition 80.0 to 30.0 mol $ ZnO, 5.0 to 20.0 moles of Cr ₃ O ₅ and 15.0 to 50.0 mole percent of at least that a third metal oxide. 8. A moisture-sensitive element according to claim 7, characterized by the composition 60.0 MoIjS ZnO 10.0 moles # Cr ₂ O ₃ and 30.0 moles $ on the at least one third metal oxide. KRE / bk 409885/1102