Thermoreflectance imaging is a powerful technique to yield high speed thermal imaging of objects. However, when the material or device being measured is transparent to the probe light, the surface temperature cannot he reliably measured. The compositions, methods, and systems discussed herein address these and other needs.
In accordance with the purposes of the disclosed compositions, methods, and systems as embodied and broadly described herein, the disclosed subject matter relates to electrically resistive films that are reflective to one or more wavelengths of light from 400 nm to 1500 nm, e.g., a thermoreflectance enhancement coating, and methods of making and use thereof.
Additional advantages of the disclosed compositions, systems, and methods will he set forth in part in the description which follows, and in part will be obvious from the description. The advantages of the disclosed compositions, systems, and methods will be realized and attained by means of the elements and combinations particularly pointed out in the appended claims. It is to be understood that both the foregoing general description and the following detailed description are exemplary and explanatory only and are not restrictive of the disclosed compositions, systems, and methods, as claimed.
The details of one or more embodiments of the invention are set forth in the accompanying drawings and the description below. Other features, objects, and advantages of the invention will be apparent from the description and drawings, and from the claims,
The accompanying figures, which are incorporated in and constitute a part of this specification, illustrate several aspects of the disclosure, and together with the description, serve to explain the principles of the disclosure.
The compositions, methods, and systems described herein may be understood more readily by reference to the following detailed description of specific aspects of the disclosed subject matter and the Examples included therein.
Before the present compositions, methods, and systems are disclosed and described, it is to be understood that the aspects described below are not limited to specific synthetic methods or specific reagents, as such may, of course, vary. It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting.
Also, throughout this specification, various publications are referenced. The disclosures of these publications in their entireties are hereby incorporated by reference into this application in order to more fully describe the state of the art to which the disclosed matter pertains. The references disclosed are also individually and specifically incorporated by reference herein for the material contained in them that is discussed in the sentence in which the reference is relied upon.
In this specification and in the claims that follow, reference will be made to a number of terms, which shall be defined to have the following meanings.
Throughout the description and claims of this specification the word “comprise” and other forms of the word, such as “comprising” and “comprises,” means including but not limited to, and is not intended to exclude, for example, other additives, components, integers, or steps.
As used in the description and the appended claims, the singular forms “a,” “an,” and “the” include plural referents unless the context clearly dictates otherwise. Thus, for example, reference to “a composition” includes mixtures of two or more such compositions, reference to “an agent” includes mixtures of two or more such agents, reference to “the component” includes mixtures of two or more such components, and the like.
“Optional” or “optionally” means that the subsequently described event or circumstance can or cannot occur, and that the description includes instances where the event or circumstance occurs and instances where it does not.
Ranges can be expressed herein as from “about” one particular value, and/or to “about” another particular value. By “about” is meant within 5% of the value, e.g., within 4, 3, 2, or 1% of the value. When such a range is expressed, another aspect includes from the one particular value and/or to the other particular value. Similarly, when values are expressed as approximations, by use of the antecedent “about,” it will be understood that the particular value forms another aspect. It will be further understood that the endpoints of each of the ranges are significant both in relation to the other endpoint, and independently of the other endpoint.
Values can be expressed herein as an “average” value. “Average” generally refers to the statistical mean value.
By “substantially” is meant within 5%, e.g., within 4%, 3%, 2%, or 1%.
“Exemplary” means “an example of” and is not intended to convey an indication of a preferred or ideal embodiment. “Such as” is not used in a restrictive sense, but for explanatory purposes.
It is understood that throughout this specification the identifiers “first” and “second” are used solely to aid in distinguishing the various components and steps of the disclosed subject matter. The identifiers “first” and “second” are not intended to imply any particular order, amount, preference, or importance to the components or steps modified by these terms.
The term “or combinations thereof” as used herein refers to all permutations and combinations of the listed items preceding the term. For example, “A, B, C, or combinations thereof” is intended to include at least one of: A, B, C, AB, AC, BC, or ABC, and if order is important in a particular context, also BA, CA, CB, CBA, BCA, ACB, BAC, or CAB. Continuing with this example, expressly included are combinations that contain repeats of one or more item or term, such as BB, AAA, AB, BBC, AAABCCCC, CBBAAA, CABABB, and so forth. The skilled artisan will understand that typically there is no limit on the number of items or terms in any combination, unless otherwise apparent from the context.
Disclosed herein are electrically resistive films that are reflective to one or more wavelengths of light from 400 nm to 1500 nm, e.g., thermoreflectance enhancement coatings, and methods of making and use thereof.
For example, the coating can be reflective to light having one or more wavelengths of 400 nanometers (nm) or more (e.g., 405 nm or more, 410 nm or more, 415 nm or more, 420 nm or more, 425 nm or more, 430 nm or more, 435 nm or more, 440 nm or more, 445 nm or more, 450 nm or more, 455 nm or more, 460 nm or more, 465 nm or more, 470 nm or more, 475 nm or more, 480 nm or more, 485 nm or more, 490 nm or more, 495 nm or more, 500 nm or more, 505 nm or more, 510 nm or more, 515 nm or more, 520 nm or more, 525 nm or more, 530 nm or more 535 nm or more, 540 nm or more, 545 nm or more, 550 nm or more, 555 nm or more, 560 nm or more, 565 nm or more, 570 nm or more, 575 nm or more, 580 nm or more, 585 nm or more, 590 nm or more, 595 nm or more, 600 nm or more, 605 nm or more, 610 nm or more, 615 nm or more, 620 nm or more, 625 nm or more, 630 nm or more, 635 nm or more, 640 nm or more, 645 nm or more, 650 nm or more, 655 nm or more, 660 nm or more, 665 nm or more, 670 nm or more, 675 nm or more, 680 nm or more, 685 nm or more, 690 nm or more, 695 nm or more, 700 nm or more, 705 nm or more, 710 nm or more, 715 nm or more, 720 nm or more, 725 nm or more, 730 nm or more, 735 nm or more, 740 nm or more, 745 nm or more, 750 nm or more, 755 nm or more, 760 nm or more, 765 nm or more, 770 nm or more, 775 nm or more, 780 nm or more, 785 nm or more, 790 nm or more, 795 nm or more, 800 nm or more, 805 nm or more, 810 nm or more, 815 nm or more, 820 nm or more, 825 nm or more, 830 nm or more, 835 nm or more, 840 nm or more, 845 nm or more, 850 nm or more, 855 nm or more, 860 nm or more, 865 nm or more, 870 nm or more, 875 nm or more, 880 nm or more, 885 nm or more, 890 nm or more, 895 nm or more, 900 nm or more, 905 nm or more, 910 nm or more, 915 nm or more, 920 nm or more, 925 nm or more, 930 nm or more, 935 nm or more, 940 nm or more, 945 nm or more, 950 nm or more, 955 nm or more, 960 nm or more, 965 nm or more, 970 nm or more, 975 nm or more, 980 nm or more, 985 nm or more, 990 nm or more, 995 nm or more, 1000 nm or more, 1005 nm or more, 1010 nm or more, 1015 nm or more, 1020 nm or more, 1025 nm or more, 1030 nm or more, 1035 nm or more, 1040 nm or more, 1045 nm or more, 1050 nm or more, 1055 nm or more, 1060 nm or more, 1065 nm or more, 1070 nm or more, 1075 nm or more, 1080 nm or more, 1085 nm or more, 1090 nm or more, 1095 nm or more, 1100 nm or more, 1105 nm or more, 1110 nm or more, 1115 nm or more, 1120 nm or more, 1125 nm or more, 1130 nm or more, 1135 nm or more, 1140 nm or more, 1145 nm or more, 1150 nm or more, 1155 nm or more, 1160 nm or more, 1165 nm or more, 1170 nm or more, 1175 nm or more, 1180 nm or more, 1185 nm or more, 1190 nm or more, 1195 nm or more, 1200 nm or more, 1205 nm or more, 1210 nm or more, 1215 nm or more, 1220 nm or more, 1225 nm or more, 1230 nm or more, 1235 nm or more, 1240 nm or more, 1245 nm or more, 1250 nm or more, 1255 nm or more, 1260 nm or more, 1265 nm or more, 1270 nm or more, 1275 nm or more, 1280 nm or more, 1285 nm or more, 1290 nm or more, 1295 nm or more, 1300 nm or more, 1305 nm or more, 1310 nm or more, 1315 nm or more, 1320 nm or more, 1325 nm or more, 1330 nm or more, 1335 nm or more, 1340 nm or more, 1345 nm or more, 1350 nm or more, 1355 nm or more, 1360 nm or more, 1365 nm or more, 1370 nm or more, 1375 nm or more, 1380 nm or more, 1385 nm or more, 1390 nm or more, 1395 nm or more, 1400 nm or more, 1405 nm or more, 1410 nm or more, 1415 nm or more, 1420 nm or more, 1425 nm or more, 1430 nm or more, 1435 nm or more, 1440 nm or more, 1445 nm or more, 1450 nm or more, 1455 nm or more, 1460 nm or more, 1465 nm or more, 1470 nm or more, 1475 nm or more, 1480 nm or more, 1485 nm or more, 1490 nm or more, or 1495 nm or more).
In some examples, the coating can be reflective to light having one or more wavelengths of 1500 nanometers (am) or less (e,g., 1495 nm or less, 1490 nm or less, 1485 nm or less, 1480 nm or less, 1475 nm or less, 1470 nm or less, 1465 am or less, 1460 nm or less, 1455 nm or less, 1450 nm or less, 1445 nm or less, 1440 nm or less, 1435 nm or less, 1430 nm or less, 1425 nm or less, 1420 nm or less, 1415 nm or less, 1410 nm or less, 1405 nm or less, 1400 nm or less, 1395 nm or less, 1390 nm or less, 1385 nm or less, 1380 nm or less, 1375 nm or less, 1370 nm or less, 1365 nm or less, 1360 nm or less, 1355 nm or less, 1350 nm or less, 1345 nm or less, 1340 nm or less, 1335 nm or less, 1330 nm or less, 1325 nm or less, 1320 nm or less, 1315 nm or less, 1310 nm or less, 1305 nm or less, 1300 nm or less, 1295 nm or less, 1290 nm or less, 1285 nm or less, 1280 nm or less, 1275 nm or less, 1270 nm or less, 1265 nm or less, 1260 nm or less, 1255 nm or less, 1250 nm or less, 1245 nm or less, 1240 nm or less, 1235 nm or less, 1230 nm or less, 1225 nm or less, 1220 nm or less, 1215 nm or less, 1210 nm or less, 1205 nm or less, 1200 nm or less, 1195 nm or less, 1190 nm or less, 1185 nm or less, 1180 nm or less, 1175 nm or less, 1170 nm or less, 1165 nm or less, 1160 nm or less, 1155 nm or less, 1150 nm or less, 1145 nm or less, 1140 nm or less, 1135 nm or less, 1130 nm or less, 1125 nm or less, 1120 nm or less, 1115 nm or less, 1110 nm or less, 1105 nm or less, 1100 nm or less, 1095 nm or less, 1090 nm or less, 1085 nm or less, 1080 nm or less, 1075 nm or less, 1070 nm or less, 1065 nm or less, 1060 nm or less, 1055 nm or less, 1050 nm or less, 1045 nm or less, 1040 nm or less, 1035 nm or less, 1030 nm or less, 1025 nm or less, 1020 nm or less, 1015 nm or less, 1010 nm or less, 1005 nm or less, 1000 nm or less, 995 nm or less, 990 nm or less, 985 nm or less, 980 nm or less, 975 nm or less, 970 nm or less, 965 nm or less, 960 nm or less, 955 nm or less, 950 nm or less, 945 nm or less, 940 nm or less, 935 nm or less, 930 nm or less, 925 nm or less, 920 nm or less, 915 nm or less, 910 nm or less, 905 nm or less, 900 nm or less, 895 nm or less, 890 nm or less, 885 nm or less, 880 nm or less, 875 nm or less, 870 nm or less, 865 nm or less, 860 nm or less, 855 nm or less, 850 nm or less, 845 nm or less, 840 nm or less, 835 nm or less, 830 nm or less, 825 nm or less, 820 nm or less, 815 nm or less, 810 nm or less, 805 nm or less, 800 nm or less, 795 nm or less, 790 nm or less, 785 nm or less, 780 nm or less, 775 nm or less, 770 nm or less, 765 nm or less, 760 nm or less, 755 nm or less, 750 nm or less, 745 nm or less, 740 nm or less, 735 nm or less, 730 nm or less, 725 nm or less, 720 nm or less, 715 nm or less, 710 nm or less, 705 nm or less, 700 nm or less, 695 nm or less, 690 nm or less, 685 nm or less, 680 nm or less, 675 nm or less, 670 nm or less, 665 nm or less, 660 nm or less, 655 nm or less, 650 nm or less, 645 nm or less, 640 nm or less, 635 nm or less, 630 nm or less, 625 nm or less, 620 nm or less, 615 nm or less, 610 nm or less, 605 nm or less, 600 nm or less, 595 nm or less, 590 nm or less, 585 nm or less, 580 nm or less, 575 nm or less, 570 nm or less, 565 nm or less, 560 nm or less, 555 nm or less, 550 nm or less, 545 nm or less, 540 nm or less, 535 nm or less, 530 nm or less, 525 nm or less, 520 nm or less, 515 nm or less, 510 nm or less, 505 nm or less, 500 nm or less, 495 nm or less, 490 nm or less, 485 nm or less, 480 nm or less, 475 nm or less, 470 nm or less, 465 nm or less, 460 nm or less, 455 nm or less, 450 nm or less, 445 nm or less, 440 nm or less, 435 nm or less, 430 nm or less, 425 nm or less, 420 nm or less, 415 nm or less, 410 nm or less, or 405 nm or less).
The one or more wavelengths of light reflected by the coating can range from any of the minimum values described above to any of the maximum values described above. For example, the coating can be reflective to light having one or more wavelengths from 400 nm to 1500 nm (e.g., from 400 to 950 nm, from 950 nm to 1500 nm, from 400 nm to 500 nm, from 500 nm to 600 nm, from 600 nm to 700 nm, from 700 nm to 800 nm, from 800 nm to 900 nm, from 900 nm to 1000 nm, from 1000 nm to 1100 nm, from 1100 nm to 1200 nm, from 1200 nm to 1300 nm, from 1300 nm to 1400 nm, from 1400 nm to 1500 nm, from 400 nm to 1400 nm, from 400 nm to 1300 nm, from 400 nm to 1200 nm, from 400 nm to 1100 nm, from 400 nm to 1000 nm, from 400 nm to 900 nm, from 400 nm to 800 nm, from 400 nm to 700 nm, from 400 nm to 600 nm, from 500 nm to 1500 nm, from 600 nm to 1500 nm, from 700 nm to 1500 nm, from 800 nm to 1500 nm, from 900 nm to 1500 nm, from 1000 nm to 1500 nm, from 1100 nm to 1500 nm, from 1200 nm to 1500 nm, from 1300 nm to 1500 nm, from 500 nm to 1400 nm, from 600 nm to 1300 nm, from 500 nm to 1200 nm, from 600 nm to 1100 nm, or from 700 nm to 1000 nm).
The thermoreflectance enhancement coatings can, for example, comprise a transition metal dichalcogenide or a thermochromic polymer.
As used herein, a “transition metal dichalcogenide” refers to a compound comprising a transition metal and two chalcogen atoms. As used herein, a “transition metal” refers to any element from groups 3-12, such as Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd, Ag, Cd, La, Hf, Ta, W, Re, Os, Ir, Pt, Au, Hg, and Ac. As used herein a “chalcogen” refers to any element from group 16, such as oxygen, sulfur, selenium, tellurium, and polonium. As such, transition metal chalcogenides can include transition metal oxides, transition metal sulfides, and transition metal selenides, among others. For example, the transition metal dichalcogenide can comprise MoS2, WS2, MoSe2, WSe2, MoTe2, WTe2, or a combination thereof. In some examples, the transition metal dichalcogenide comprises MoS2, MoSe2, WS2, WSe2, or a combination thereof. In some examples, the transition metal dichalcogenide comprises MoS2.
As used herein a “thermochromic polymer” can comprise any polymer with thermochromic properties. Thermochromic properties can, for example, include control of optical properties such as optical transmission, absorption, reflectance, and/or emittance in a continual manner on application of a temperature. In some examples, the thermochromic polymer can comprise poly(ProDOT-alt-EDOT2) (PE2).
The coating can, for example, have an average thickness of 10 nm or more (e.g., 15 nm or more, 20 nm or more, 25 nm or more, 30 nm or more, 35 nm or more, 40 nm or more, 45 nm or more, 50 nm or more, 60 nm or more, 70 nm or more, 80 nm or more, 90 nm or more, 100 nm or more, 125 nm or more, 150 nm or more, 175 nm or more, 200 nm or more, 225 nm or more, 250 nm or more, 275 nm or more, 300 nm or more, 325 nm or more, 350 nm or more, 400 nm or more, 450 nm or more, 500 nm or more, 550 nm or more, 600 nm or more, 650 nm or more, 700 nm or more, 750 nm or more, 800 nm or more, 850 nm or more, 900 nm or more, or 950 or more). In some examples, the coating can have an average thickness of 1000 nm or less (e.g., 950 nm or less, 900 nm or less, 850 nm or less, 800 nm or less, 750 nm or less, 700 nm or less, 650 nm or less, 600 nm or less, 550 nm or less, 500 nm or less, 450 nm or less, 400 nm or less, 350 nm or less, 325 nm or less, 300 nm or less, 275 nm or less, 250 nm or less, 225 nm or less, 200 nm or less, 175 nm or less, 150 nm or less, 125 nm or less, 100 nm or less, 90 nm or less, 80 nm or less, 70 nm or less, 60 nm or less, 50 nm or less, 45 nm or less, 40 nm or less, 35 nm or less, 30 nm or less, 25 nm or less, 20 nm or less, or 15 nm or less). The average thickness of the coating can range from any of the minimum values described above to any of the maximum values described above. For example, the coating can have an average thickness of 10 nm to 1000 nm (e.g., from 10 nm to 500 nm, from 500 nm to 1000 nm, from 10 nm to 200 nm, from 200 nm to 400 nm, from 400 nm to 600 nm, from 600 nm to 800 nm, from 800 nm to 1000 nm, from 25 nm to 1000 nm, from 10 nm to 900 nm, from 25 nm to 900 nm, or from 200 nm to 350 nm). Average thickness” and “mean thickness” are used interchangeably herein. Average thickness can be measured using methods known in the art, such as evaluation by profilometry, cross-sectional electron microscopy, atomic force microscopy (AFM), ellipsometry, or combinations thereof.
In some examples, the coating has an average coefficient of thermoreflectance (Cth) of −2×10−4 K−1 or less (e.g., −2.05×10−4 K−1 or less, −2.1×10−4 K−1 or less, −2.15×10−4 K−1 or less, −2.2×10−4 K−1 or less, −2.25×10−4 K−1 or less, −2.3×10−4 K−1 or less, −2.35×10−4 K−1 or less, −2.4×10−4 or less, −2.45×10−4 K−1 or less, −2.5×10−4 K−1 or less, −2.55×10−4 K−1 or less, −2.6×10−4 K−1 or less, −2.65×10−4 K−1 or less, −2.7×10−4 K−1 or less, −2.75×10−4 K−1 or less, −2.8×10−4 K−1 or less, −2.85×10−4 K−1 or less, −2.9×10−4 K−1 or less, −3×10−4 K−1 or less, −3.1×10−4 K−1 or less, −3.2×10−4 K−1 or less, −3.3×10−4 K−1 or less, −3.4×10−4 K−1 or less, −3.5×10−4 K−1 or less, −3.6×10−4 K−1 or less, −3.7×10−4 K−1 or less, −3,8×10−4 K−1 or less, −3.9×10−4 K−1 or less, −4×10−4K−1 or less, −4.1×10−4 K−1 or less, −4.2×10−4 K−1 or less, −4.3×10−4 K−1 or less, −4.4×10−4 K−1 or less, −4.5×10−4 K−1 or less, −4,6×10−4 K−1 or less, −4.7×10−4 K−1 or less, −4.8×10−4 K−1 or less, −4.9×10−4 K−1 or less, or −5×10−4 K−1 or less) over a temperature range (ΔT) of 10 K or more (e.g., 20 K or more, 30 K or more. 40 K or more, 50 K or more, 60 K or more, 70 K or more, 80 K or more, 90 K or more, or 100 K or more).
In some examples, the coating has an average coefficient of thermoreflectance (Cth) with an absolute value of (|Cth|) 2×10−4 K−1 or more (e.g., 2.05×10−4 K−1 or more, 2.1×10−4 K−1 or more, 2.15×10−4 K−1 or more, 2.2×10−4 K−1 or more. 2.25×10−4 K−1 or more. 2.3×10−4 K−1 or more, 2.35×10−4 K−1 or more, 2.4×10−4K−1 or more, 2.45×10−4 K−1 or more, 2.5×10−4K−1 or more, 2.55×10−4 K−1 or more, 2.6×10−4 K−1 or more, 2.65×10−4 K−1 or more, 2.7×10−4 K−1 or more, 2.75×10−4 K−1 or more, 2.8×10−4 K−1 or more, 2.85×10−4 K−1 or more, 2.9×10−4 K−1 or more, 2.95×10−4 K−1 or more. 3×10−4 K−1 or more, 3.1×10−4 K−1 or more, 3.2×10−4 K−1 or more, 3.3×10−4 K−1 or more, 3.4×10−4 K−1 or more, 3.5×10−4 K−1 or more, 3.6×10−4 K−1 or more, 3.7×10−4 K−1 or more, 3.8×10−4 K−1 or more. 3.9×10−4 K−1 or more, 4×10−4 K−1 or more, 4.1×10−4 K−1 or more, 4.2×10−4 K−1 or more, 4.3×10−4 K−1 or more, 4.4×10−4 K−1 or more, 4.5×10−4 K−1 or more, 4.6×10−4 K−1 or more. 4.7×10−4 K−1 or more. 4.8×10−4 K−1 or more, 4.9×10−4 K−1 or more, or 5×10−4 K−1 or more) over a temperature range (ΔT) of 10 K or more (e.g., 20 K or more, 30 K or more, 40 K or more, 50 K or more, 60 K or more, 70 K or more, 80 K or more, 90 K or more, or 100 K or more).
Also disclosed herein are methods of enhancing the thermoreflectance of a wide bandgap semiconductor, the method comprising depositing any of the coatings disclosed herein onto the wide bandgap semiconductor.
Depositing the coating can, for example, comprise printing (e.g., air jet printing, ink jet printing), electroplating, lithographic deposition, electron beam deposition, thermal deposition, spin coaling, drop-casting, zone casting, dip coating, blade coating, spraying, vacuum filtration, slot die coating, curtain coating, chemical vapor deposition (CVD), atomic layer deposition (ALD), physical vapor deposition (PVD), sputtering, pulsed layer deposition, molecular beam epitaxy, evaporation, or combinations thereof. In some examples, depositing the coating comprises printing, spin coating, sputtering, electron beam deposition, drop-casting, or a combination thereof.
In some examples, the methods can further comprise forming a solution comprising a solvent and the transition metal dichalcogenide or thermochromic polymer, and depositing the mixture to form the coating.
Examples of solvents include, but are not limited to, water, tetrahydrofuran (THF), N-methyl-2-pyrrolidone (NMP), dimethylformamide (DMF) N-methylformamide, formamide, ethylene glycol, polyethylene glycol, glycerol, alkane diol, ethanol, methanol, propanol, isopropanol, acetonitrile, acetone, tetraglyme, propylene carbonate, diglyme, dimethyl sulfoxide (DMSO), dimethoxyethane, dimethylacetamide, and combinations thereof.
In some examples, forming the solution can comprise dispersing the transition metal dichalcogenide or thermochromic polymer in the solvent. Dispersing the transition metal dichalcogenide or thermochromic polymer in the solvent can be accomplished by mechanical agitation, for example, mechanical stirring, shaking, vortexing, sonication (e.g., bath sonication, probe sonication, ultrasonication), and the like, or combinations thereof.
In some examples, the methods can further comprise drying the coating after deposition (e.g., air drying, spin drying, oven drying, vacuum drying, etc.).
Also disclosed herein are devices comprising a wide bandgap or ultrawide bandgap semiconductor, wherein the device further comprises the any of the thermoreflectance enhancement coatings disclosed herein deposited on the wide bandgap or ultrawide bandgap semiconductor. In some examples, the thermoreflectance enhancement coating does not significantly impact the operation of the device.
Also disclosed herein are methods of thermally imaging a wide bandgap or ultrawide bandgap semiconductor, the method comprising depositing any of the thermoreflectance enhancement coatings disclosed herein on the wide bandgap or ultrawide bandgap semiconductor and then thermally imaging the coating. Thermally imaging the coating can, for example, comprise using transient thermoreflectance imaging. In some examples, the method of thermal imaging can use a probe light having a wavelength below the bandgap of the semiconductor and being reflective to the coating. In some examples, the thermoreflectance coating can be removed from the device after thermal imaging and before use of the device.
A number of embodiments of the invention have been described. Nevertheless, it will be understood that various modifications may be made without departing from the spirit and scope of the invention. Accordingly, other embodiments are within the scope of the following claims.
The examples below are intended to further illustrate certain aspects of the systems and methods described herein, and are not intended to limit the scope of the claims.
The following examples are set forth below to illustrate the methods and results according to the disclosed subject matter. These examples are not intended to be inclusive of all aspects of the subject matter disclosed herein, but rather to illustrate representative methods and results. These examples are not intended to exclude equivalents and variations of the present invention which are apparent to one skilled in the art.
Efforts have been made to ensure accuracy with respect to numbers (e.g., amounts, temperature, etc.) but some errors and deviations should be accounted for. Unless indicated otherwise, parts are parts by weight, temperature is in ° C. or is at ambient temperature, and pressure is at or near atmospheric. There are numerous variations and combinations of measurement conditions, e.g., component concentrations, temperatures, pressures and other measurement ranges and conditions that can be used to optimize the described process.
Thermoreflectance imaging is a powerful technique to yield high speed thermal imaging of objects. One issue that arises when the surface being imaged is transparent to the probing light source, it is not always possible to know where in the object the reflectance is being generated and thus where the temperature is being measured, e.g., the surface temperature cannot be reliably measured.
By using a coating which enhances the thermoreflectance, it is possible to improve the temperature measurement while also spatially defining the measurement to the device surface. Herein, a coating was utilized to enhance thermoreflectance signals on ultrawide bandgap semiconductors where the signal is generated with light wavelengths below the bandgap of the semiconductor.
Described herein are coatings that provide surface reflectance, which is used to measure the surface temperature of a material or device, leaving the electrical and thermal properties of that material or device unaffected. These coatings are referred to as thermoreflectance enhancement coatings, since they enhance the surface reflection of the light and provide a thermoreflectance signal which can be used to measure the temperature.
Thin films are used which do not significantly impact the operation of the device on which it is applied, while also being reflective to the probe light source and/or having a lower bandgap such that it yields good thermoreflectance. Without loss of generality, layered crystalline materials such transition metal dichalcogenides (e.g., 2D materials like MoS2) and thermochromic polymers (e.g., poly(ProDOT-alt-EDOT2) (PE2)) contain these characteristics for use as thermoreflectance enhancement coatings.
This principle is demonstrated using MoS2, and poly(ProDOT-alt-EDOT2) (PE2) thin films. In this case, both films were deposited using solution processing techniques and are removable via simple bath sonication. However, other deposition techniques such as ink jet printing, spin coating, sputtering, and electron beam deposition are also possible.
Commercial applications can include thermal measurement of wide bandgap semiconductors and materials during operation.
The compositions, methods, and systems described herein allow the measurement of the operational temperature via thermoreflectance imaging of devices containing materials with bandgaps larger in energy than the energy of the probe light.
Demonstration of MoS2 Thermoreflectance Enhancement Coatings
As a demonstration, molybdenum disulfide (MoS2) films (<250 nm thick) are used as a thermoreflectance enhancement coating for the thermal imaging of wide and ultrawide bandgap electronic devices during device operation (e.g. field effect transistor). A solution containing MoS2 in suspension is coated onto the surface of the device (e.g., air jet printing, drop casting, spin coating). After deposition all solvent molecules are removed by evaporation in a vacuum oven (e.g. 200° C. under primary vacuum for 30 min). A light emitting diode (LED) with an energy above the bandgap of MoS2 and below the band gap of the device material is used to illuminate the MoS2 coated device. The reflectance (R), which is confirmed to come from the MoS2 film, is measured with a CCD camera as a function of temperature using a piezoelectric controlled heated stage and the thermoreflectance coefficient (Cth) is computed:
where ΔR/R is the relative change in reflectance observed across the temperature change ΔT. The device is then powered at ambient temperature under pulsed or steady stated conditions, the change in reflectance is measured and the Cth of the MoS2 film is used to map the temperature of the device. This enables transient and steady state thermal imaging on the surface of wide and ultrawide bandgap devices using the thermoreflectance of light that is lower in energy than the active materials bandgap.
Measuring the maximum operating temperature within the channel of ultrawide bandgap transistors is critically important because the temperature dependence of the device reliability sets operational limits such as maximum operational power. Thermoreflectance imaging (TTI) is an optimal choice to measure the junction temperature due to its sub-micron spatial resolution and sub-microsecond temporal resolution. Since TTI is an imaging technique, data acquisition is orders of magnitude faster than point measurement techniques such as Raman thermometry. Unfortunately, commercially available LED light sources used in thermoreflectance systems are limited to energies less than ˜3.9 eV which is below the handgap of many ultrawide handgap semiconductors (>4.0 eV). Therefore, the semiconductors are transparent to the probing light sources prohibiting the application of TTI. To address this thermal imaging challenge, a MoS2 coating was utilized as a thermoreflectance enhancement coating which allows for the measurement of the surface temperature of (ultra)wide bandgap materials. This coating is polycrystalline with the c-axis aligned normal to the surface and is easily removable via sonication, The method is validated using electrical and thermal characterization of GaN and AlGaN devices. It is demonstrated that this coating does not significantly influence the electrical and thermal behavior of the devices tested. A maximum temperature rise of 49 K at 0.59 W was measured within the channel of the AlGaN device, which is over double the maximum temperature rise obtained by measuring the thermoreflectance of the gate metal. The importance of accurately measuring peak operational temperature is discussed in the context of accelerated stress testing.
Introduction. The development of wide bandgap (WBG) and ultrawide bandgap (UWBG) electronics has been the focus of much research attention due to their potential to create advanced radio frequency (RF) and power devices. Materials like GaN have played a central role in this development, owing to its large bandgap (Eg=3.4 eV), high critical breakdown field (Ec), and the formation of a two-dimensional electron gas with high carrier density and mobility. These features enable high voltage and high power devices with fast switching speeds (Amano H. et al. J. Phys. D Appl. Phys. 2018, 51, 163001). Additionally, next generation UWBG systems made from AlGaN and β-Ga2O3 are being developed due to their potential for increased performance over lower handgap semiconductors, including GaN. Factors like Johnson Figure of Merit (JFOM=νsatEc/2π where νsat is the saturation velocity and Ec is the critical field) are used to compare semiconductor materials for their potential to create high frequency transistors (Johnson E O. Semiconductor Devices: Pioneering Papers, 1991, p. 295-302). The Lateral Figure of Merit (LFOM) is used to compare the theoretically achievable switching performance of lateral transistor architectures (Coltrin M E et al. ECS J. Solid State Sci. Technol. 2017, 6, S3114-S3118). The LFOM can he expressed as qμnsEc2 where q is the charge density, μ is the channel mobility, and ns is the sheet charge density. Finally, the Baliga Figure of Merit (BFOM) is used for unipolar vertical devices (Baliga B J. IEEE Electron Device Lett. 1989, 10, 455-457). BFOM is given by εμEg3 where ε is the permittivity of free space and Eg is the bandgap. In all cases, these FOMs scale with the critical electric field, Ec, which scales nonlinearly with the handgap energy (Eg) of the semiconductor (Ec∝Eg2). Thus, as the bandgap energy increases, large increases in the FOMs arc seen which suggests that WBG and UWBG semiconductors may have a distinct advantage of low bandgap semiconductors like Si for both RF and power switching applications. Another advantage for materials like β-Ga2O3 (Eg˜4.8 eV) lies in the fact that high crystalline quality substrates can be grown from the melt phase in a manner similar to Si. This is promising since it may yield a pathway to scalable production of low-cost semiconductor substrates for the grow to UWBG β-Ga2O3 devices.
One of the challenges that arises from WBG and UWBG devices is that the maximum output power is limited by the high channel temperature induced by localized Joule-heating as a result of the high power densities expected in these devices. The high channel temperatures degrade the device performance and reliability and is thus a major concern (Yates L e. al. IEEE Compd. Semicond. Integr. Circuit Symp. (CSICS) 2016, p. 1-4; Won Y et al. IEEE Trans. Components, Packag. Manuf. Technol. 2015, 5, 737-744). This has led to innovative methods for the thermal management of WBG and UWBG devices which includes the integration of diamond substrates (Cheng Z et al. Appl. Phys. Lett. 2020, 116, 062105; Noh J et al. IEEE J. Electron Devices Soc. 2019. 7, 914-918) and heat spreaders (Yates L et al. IEEE Compd. Semicond. Integr. Circuit Symp. (CSICS) 2016. p. 1-4), high thermal conductivity AlN layers (Pavlidis G et al. IEEE Electron Device Lett. 2019, 40, 1060-1063), flip-chip bonding (Sun J et al. IEEE Electron Device Lett. 2003, 24, 375-377), and double-sided cooling architectures (Montgomery R H et al. J. Appl. Phys. 2021, 129, 085301) to enable high power device performance while limiting the device junction temperature. A critical aspect of these advanced cooling approaches has been the development and utilization of methods that can accurately measure the device temperature to verify its thermal performance. Additionally, accurately measuring the maximum device temperature during operation is critical for predicting reliability and electro-thermal co-design. A simple Arrhenius relationship is commonly used to predict device lifetime (JEP118A. Guidelines for GaAs MMIC PHEMT/MESFET and HBT Reliability Accelerated Life Testing. JEDEC Publication (2018); Cooper M S. IEEE Trans. Components Packag. Technol. 2005, 28, 561-563). Therefore, relatively small errors in the measurement of the maximum device temperature, and in-turn the thermal resistance of a devices can lead to dramatic errors in the estimation of lifetime by accelerated testing methods, particularly when the projecting to different operating conditions (Heller E R. IEEE Trans. Electron Devices 2008, 55, 2554-2560).
A number of thermal metrology methods have been developed which have been used to measure the junction temperature of lateral and vertical devices made from WBG and UWBG devices. Methods like Raman spectroscopy have been widely used due to its ability to measure the steady state and transient temperature rise in GaN devices with submicron spatial resolution (Maize K et al. 2014 IEEE Compound Semiconductor Integrated Circuit Symposium (CSICS) 2014, p. 1-8). This method typically employs a laser source that is focused through a microscope objective to achieve the high spatial resolution and is thus a single point measurement technique. For materials like GaN, AlGaN, and β-Ga2O3, Raman thermography is often performed using sub-bandgap laser energies which means that the semiconductor is transparent to the laser wavelength. Thus, Raman scattering takes place over a significant depth of the semiconductor layer and thus provides an average temperature over the interaction volume. This inherently means Raman provides an average temperature of any thermal gradients that exist in that volume. Methods utilizing Raman active nanoparticles (Lundh J S et al. Appl. Phys. Lett. 2019, 115. 153503) and 2D materials (Lundh J S et al. ACS Appl. Electron. Mater. 2020, 2, 2945-2953) deposited on the surface of semiconductors have also been used which allow for the measurement of surface temperatures by Raman spectroscopy. Gate resistance thermometry has also been applied to lateral devices which allows for the measurement of channel temperatures by monitoring the temperature dependent resistance of the gate metal (Pavlidis G et al. IEEE Trans. Electron Devices 2017, 64, 78-83). Previous research has shown that this method can yield high resolution transient and steady state temperature measurements but confined to the location of the gate. IR thermography provides a full field method to measure the temperature of devices (Sarua A et al. IEEE Trans. Electron Devices 2006, 53, 2438-2447). However, challenges exist in the direct measurement of the device channel of WBG and UWBG devices since they are transparent to IR wavelengths. Thus, when applying IR to the channel regions only qualitative measurements of temperature can be measured using IR thermography since errors can be easily introduced. Another full field method that has been developed is Transient Thermoreflectance Imaging (TTI) which depends on the temperature dependence of reflectivity of light from the surface of the semiconductor devices (Kendig D et al. 2016-22nd Int. Work. Therm. Investig. ICs Syst. (THERMINIC) p. 115-120). This method has been applied to the measurement of the metal contacts in UWBG devices made from AlGaN (Lundh J S et al. Appl. Phys. Lett. 2019, 115, 153503). However, it suffers from the same issues as Raman and IR thermography when applied to the channel region. The readily available light sources are commonly below the bandgap energy and thus the channels are transparent to the light sources used for thermal imaging, particularly for UWBG materials (
Herein, a method is presented to overcome the challenges of applying TTI to WBG and UWBG device channels by deploying a low bandgap layered material to the surface of the devices. Herein, MoS2 coatings are used which enhance the thermoreflectance from the surface of the WBG and UWBG materials while not impacting the electrical performance of the devices (
Devices. Two types of devices were used to validate the MoS2 thermoreflectance coating: (i) a GaN on Si transition line method device (TLM,
MoS2 Coating Procedure and Film Characterization.
Gravity drop coating. MoS2 in a suspension containing IPA and acetone was obtained from CRC Industries (Product No. 03084). The as received suspension was sonicated for 90 min and filtered to remove agglomerations. Just before film deposition, the suspension was sonicated again for 5 minutes. MoS2 films were deposited by supporting the device wafer at a ˜45° angle, oriented such that a drop will roll across the channel, perpendicular to the direction of charge transport. This avoids agglomeration of flakes at the edge of the electrodes. A micropipette was used to deposit a drop on the wafer which then rolls over the device to be measured, not allowing the MoS2 suspension to pool on top of the device. The orientation of this gravity drop coating procedure can be important for achieving uniform high reflectivity. The film was then annealed in a vacuum oven at 200° C., under roughing vacuum (˜102 torr) to remove any remaining solvent molecules. An MoS2 film was cast onto a 100 Si wafer (SiO2 surface) using the same gravity drop coating and annealing technique. This test film was used to characterize the particle size, orientation, film thickness, uniformity, and chemical analysis.
X-ray photoelectron spectroscopy (XPS). XPS was used to characterize the deposited MoS2 films
Particle size and orientation. The MoS2 film on Si was also used to obtain a characteristic size and particle orientation via X-ray diffraction (XRD). XRD in Bragg-Brentano geometry along with refinements (using GSAS-II (Toby B H et al. J. Appl. Crystallogr. 2013, 46, 544-549)) were used to characterize the size and orientation of the MoS2 particles in the coating (
Raman. Raman spectroscopy was used for film characterization on a Renishaw InVia Micro-Raman system. The Ar+ laser wavelength is 488 nm. The objective is a Leica 0.50 NA 50× with 1.19 μm theoretical diffraction-limited spot size. The acquisition time is 30 s with 5 accumulations. Since the film contained highly aligned particles and only the [002] XRD peak was observed, the presence of the characteristic MoS2 E2g1 and A1g peaks provide additional chemical verification through optical phonon properties.
Thickness and uniformity. After deposition and annealing the thickness and uniformity were characterized. The thicknesses of the films were then measured using a Bruker DektakXT stylus profilometer, and the region of interest was checked for pooling an agglomeration of MoS2. A small scratch was made in the film with a needle probe and the step height from substrate to film was used to measure the thickness. The film thickness on the devices under testing which was between 200 nm to 350 nm.
Atomic force microscopy (AFM) was used to measure film uniformity (
Thermoreflectance thermal imaging (TTI). A Microsanj NT220B was used for the coefficient of thermoreflectance (Cth) calibration and measurement of temperature rise (ΔT). Values for Cth were measured by averaging the relative change in reflectivity (ΔR/R) across at least five hot-cold temperature cycles with a magnitude of ΔT, where ΔRR=CthΔT. The Cth of the MoS2 film which was deposited on the GaN device is shown in
A 50× Leica objective lens was used which results in an image resolution of 0.108 μm per pixel. This lens exhibits low UV absorption such that it can be used with both the 530 and 365 nm LED. A 365 nm band pass filter was used to reduce the bandwidth of the 365 nm LED and increase the signal to noise ratio (Pavlidis G et al. IEEE Transactions on Electron Devices 2020, 67(3), 822-827). Image filtering was performed in sanjANALYZER. Pixels were binned into 4×4 blocks and a 5×5 median filter (which assigns the median value of a moving 5×5 pixel box to the central pixel) was used. By analyzing the data with and without image filtering, it was confirmed that the image filtering does not influence the measured temperature but decreases the measurement standard deviation. Therefore, spatial resolution is sacrificed to reduce the standard deviation of the temperature rise, without affecting the resulting temperature measurements. The resolution of the measurement after image filtering was 0.432 μm. Both the CCD and ΔT images in
Both GaN and AlGaN devices were measured under pulsed conditions using a 30% duty cycle and a 100 μs period. The AlGaN MOSHFET drain-source voltage was VDS=20 V in the on state and VDS=0 V in the off state. The gate-source voltage was VGS=0 V in the on state and VGS=−12 V in the off state. The GaN device had a VDS=15 V on state, a VDS=0 V off state and was a TLM structure so therefore had no gate. The power driven through the AlGaN device in the on state was 0.59 W. The power driven through the GaN TLM device in the on state was 0.86 W. All thermal images were taken at 15 μs into the 30 μs pulse, which was determined to be pseudo steady state conditions. An example of transient pulse data is shown in
Results
Electrical properties. The electrical properties of the devices were characterized before and after application of the MoS2 film, to ensure the coating does not influence the electrical behavior of the device.
While the IDS and IGS values for the AlGaN device were unchanged, there is motivation for a stricter test to detect any current leakage that may occur through the MoS2 film.
Thermal Imaging
GaN TLM. The thermal imaging of the GaN TLM device is shown in
Now TTI using a 530 nm before and after the MoS2 coating is applied was compared. When using a 530 nm LED, the Max ΔT obtained without the coating is nearly half that obtained when the MoS2 coating is used. As can be seen in the device layer structure provided in
AlGaN MOSHFET. All layers of AlGaN device structure are transparent to both 530 nm and 365 nm LEDs. The only location where a thermoreflectance signal can be obtained without the MoS2 coating is on top of the gate metal (
The AlGaN device was powered at various VDS conditions, keeping the pulse conditions and VGS constant.
From this data two device thermal resistances can he obtained: (i) from data without the use an MoS2 coating using the maximum gate metal temperature and (ii) from data with an MoS2 coating using the maximum device temperature which occurs within channel. These two thermal resistances are given in
Implications for reliability testing. When developing a new RF or power electronic device, accelerated testing can he an essential tool to estimate device reliability (Heller E R. IEEE Trans. Electron Devices 2008, 55, 2554-2560). Standards have been established for established technologies based on Si (JEP122H. Failure Mechanisms and Models for Semiconductor Devices. JEDEC Publication (2016)) and GaAs (JEP118A. Guidelines for GaAs MMIC PHEMT/MESFET and HBT Reliability Accelerated Life Testing. JEDEC Publication (2018)). As knowledge matures it can be possible to write a generalized relationships that may contain variables pertinent to the physics of failure such as temperature, current, and electrical field (JEP122H. Failure Mechanisms and Models for Semiconductor Devices. JEDEC Publication (2016)). For less mature devices, however, it is common to first model time to failure (t) using an Arrhenius relationship (Cooper M S. IEEE Trans. Components Packag. Technol. 2005, 28, 561-563):
where kB is the Boltzmann constant, and T0 is the reference temperature (taken to be ambient temperature in
The acceleration factor is given by:
and is shown in
Conclusion. Thermoreflectance imaging is a promising tool enabling electro-thermal co-design which can accelerate the development of radio frequency and power electronics. However, its application to WBG and UWBG devices can be limited since the transistor channel is often transparent to available light sources. A coating was developed herein which enhances the surface reflection from the device without measurably impacting the devices electrical or thermal properties, enabling the measurement of device operating temperature. This technology broadens the applicability of thermoreflectance imaging to the rapidly emerging industry of UWBG transistors.
Overview. Thermochromic polymers are a class of materials that could be used for thermoreflectance enhancement coatings. Polymer films commonly exhibit low thermal and electrical conductivity (when left undoped), such that they are expected to minimally effect the electrical and thermal properties of a material or device it is deposited on. However, the polymer must have a thermochromic effect, such that the reflectance changes with temperature and provides sufficient thermoreflectance signal. The thermoreflectance coefficient (Cth) properties of a P(ProDOT-ald-EDOT2) (PE2,
The data presented here shows that thermochromic polymers, such as PE2, could be used as a thermoreflectance enhancement coating.
Methods
Material synthesis and deposition. The synthesis and deposition process of the PE2 films is detailed by Ponder et al. (Ponder J F et al. Adv. Energy Mater. 2019, 9, 1-7). The film measured here is approximately 0.5 μm thick and was blade coated on a transparent glass slide.
Thermoreflectance. A Microsanj NT220B was used for measurement of Cth. Values for Cth were measured by averaging the ΔR/R values of three hot-cold temperature cycles with a magnitude of ΔT. Thermal paste was used to thermally connect the glass slide to the heated stage. A scratch was made on the film exposing the transparent glass slide, thermal paste, and copper hot plate underneath. A 530 nm LED was used.
Results. The CCD image of the film and scratch are shown in
Plan-Perform 1) IV measurements, 2) Cth measurements, and 3) pulse thermal measurements on GaN device that is i) uncoated, ii) coated with molylube, and iii) coated with MoS2.
Uncoated measurements. The 20 μm TLM is shown up and to the right of the “+” sign in
The same pulse metrics were then used for Device #2. Thermal imaging of Device #2 is shown in
The same pulse metrics were then used for Device #3. Thermal imaging of Device #3 is shown in
Coatings. For the coatings, Molylube was sonicated for 100 minutes. The sonication gives a good MoS2 suspension. Immediately prior to drop coating, the suspension was sonicated for another 3 minutes. The devices were then coated with the Molylube using a gravity drop coating method. A drop of the Molylube suspension was placed on the device and dispersed over the area of interest using gravity.
Additional devices were coated using Sonal MoS2/IPA/Tp using a drop coating method. A drop of the Sonal MoS2/IPA/Tp was placed on the device and allowed to set. The Sonal MoS2/IPA/Tp was a very thin solution, therefore gravity drop coating would not have deposited a sufficient coating.
Further devices were coated using Sonal MoS2/IPA using a drop coating method. A drop of the Sonal MoS2/IPA was placed on the device and allowed to set. The Sonal MoS2/IPA was a very thin solution, therefore gravity drop coating would not have deposited a sufficient coating.
A photograph of the solutions used to coat the devices are shown in
After the coatings were applied, the devices were placed in a vacuum oven at 120° C. A rough pump vacuum (24 inHg) was then applied. Subsequently, the vacuum oven was heated to 200° C. in 30 minutes. The furnace was then powered off and allowed to cool while leaving the vacuum on.
Coated measurements. TTI of sample coated with Molylube is shown in
Other advantages which are obvious and which are inherent to the invention will be evident to one skilled in the art. It will be understood that certain features and sub-combinations are of utility and may be employed without reference to other features and sub-combinations. This is contemplated by and is within the scope of the claims. Since many possible embodiments may be made of the invention without departing from the scope thereof, it is to be understood that all matter herein set forth or shown in the accompanying drawings is to be interpreted as illustrative and not in a limiting sense.
The compositions, systems, and methods of the appended claims are not limited in scope by the specific compositions, system, and methods described herein, which are intended as illustrations of a few aspects of the claims and any methods that are functionally equivalent are intended to fall within the scope of the claims. Various modifications of the compositions, systems, and methods in addition to those shown and described herein are intended to fall within the scope of the appended claims. Further, while only certain representative composition elements, system elements, and method steps disclosed herein are specifically described, other combinations of the composition elements, system elements, and method steps also are intended to fall within the scope of the appended claims, even if not specifically recited. Thus, a combination of steps, elements, components, or constituents may be explicitly mentioned herein or less, however, other combinations of steps, elements, components, and constituents are included, even though not explicitly stated.
This application claims the benefit of priority to U.S. Provisional Application No. 63/211,834 filed Jun. 17, 2021, which is hereby incorporated herein by reference in its entirety.
This invention was made with government support under Grant No. FA8075-14-D-0025 awarded by the Department of Defense. The government has certain rights in the invention.
Number | Date | Country | |
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63211834 | Jun 2021 | US |