Surface ZnSe:Ca layers with hole conductivity
The authors investigate the effect of treating n-ZnSe substrates with boiling aqueous Ca(NO₃)₂ suspension on their electrical and luminescent properties. Base substrates were cut from bulk pure zinc selenide crystals grown from a stoichiometric melt by the Bridgman method. It was found that the Ca-d...
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| Опубліковано в: : | Технология и конструирование в электронной аппаратуре |
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| Дата: | 2019 |
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Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України
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| Цитувати: | Surface ZnSe:Ca layers with hole conductivity / V.P. Makhniy, M.M. Berezovskiy, O.V. Kinzerska, V.V. Melnyk // Технология и конструирование в электронной аппаратуре. — 2019. — № 3-4. — С. 31-35. — Бібліогр.: 17 назв. — англ. |
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Digital Library of Periodicals of National Academy of Sciences of Ukraine| _version_ | 1860066448238444544 |
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| author | Makhniy, V.P. Berezovskiy, M.M. Kinzerska, O.V. Melnyk, V.V. |
| author_facet | Makhniy, V.P. Berezovskiy, M.M. Kinzerska, O.V. Melnyk, V.V. |
| citation_txt | Surface ZnSe:Ca layers with hole conductivity / V.P. Makhniy, M.M. Berezovskiy, O.V. Kinzerska, V.V. Melnyk // Технология и конструирование в электронной аппаратуре. — 2019. — № 3-4. — С. 31-35. — Бібліогр.: 17 назв. — англ. |
| collection | DSpace DC |
| container_title | Технология и конструирование в электронной аппаратуре |
| description | The authors investigate the effect of treating n-ZnSe substrates with boiling aqueous Ca(NO₃)₂ suspension on their electrical and luminescent properties. Base substrates were cut from bulk pure zinc selenide crystals grown from a stoichiometric melt by the Bridgman method. It was found that the Ca-doping of the substrates causes an almost complete “quenching” of the low-energy orange emission band with a maximum near hωmax ≈ 1,95 eV and a significant increase in the efficiency of the edge blue luminescence band.
Исследовано влияние обработки подложек n-ZnSe в кипящей водной суспензии соли Ca(NO₃)₂ на их элек-трические и люминесцентные свойства.
Досліджено вплив обробки підкладинок n-ZnSe в киплячій водній суспензії солі Ca(NO₃)₂ на їхні електричні та люмінесцентні властивості.
|
| first_indexed | 2025-12-07T17:07:56Z |
| format | Article |
| fulltext |
Tekhnologiya i Konstruirovanie v Elektronnoi Apparature, 2019, No 3–4
31ISSN 2225-5818
MATERIALS OF ELECTRONICS
1
UDC 621.315.529
Dr. Sc. V. P. MAKHNIY, Ph. D. M. M. BEREZOVSKIY,
Ph. D. O. V. KINZERSKA, Ph. D. V. V. MELNYK
Ukraine, Yuri Fedkovych Chernivtsy National University
E-mail: oksanakinzerska@gmail.com, vpmakhniy@gmail.com
SURFACE ZnSe:Ca LAYERS
WITH HOLE CONDUCTIVITY
Despite the fact that zinc selenide has all the
necessary physical and technological parameters
for creating devices and instruments for short-wave
electronics, this material still remains outside the
scope of mainstream research. The main reason
for this is that obtaining crystals and (or) lay-
ers with hole conductivity and preferential edge
luminescence in the room temperature range is
technologically difficult [1]. This is due to the
large number of intrinsic and uncontrollable im-
purity defects, as well as the tendency of II—VI
compounds to self-compensate, which ultimately
leads to preferential electron conductivity of
ZnSe [2]. Moreover, a theoretical analysis of the
defect formation mechanisms in cadmium and
zinc sulfoselenides allowed the authors of [3] to
determine the temperature value (700 К), above
which it is impossible to obtain impurity hole
conductivity in these materials using traditional
equilibrium methods. In such a case, therefore,
p-type layers must be created by lower-temperature
nonequilibrium methods — laser annealing, ion
implantation, annealing in activated chalcogen va-
pors (or a combination thereof) [2]. A significant
breakthrough in obtaining p-ZnSe was made by
the authors of [4, 5], who suggested doping ZnSe
layers created by molecular-beam epitaxy with
nitrogen, activated by a radio-frequency discharge.
It is this technology that made it possible to cre-
ate the first blue-green laser structures based on
II—VI compounds [6].
Further studies have shown that the efficiency
of doping with the desired type of impurity (ac-
The authors investigate the effect of treating n-ZnSe substrates with boiling aqueous Ca(NO3)2 suspension
on their electrical and luminescent properties. Base substrates were cut from bulk pure zinc selenide
crystals grown from a stoichiometric melt by the Bridgman method. It was found that the Ca-doping
of the substrates causes an almost complete “quenching” of the low-energy orange emission band with a
maximum near ħωmax ≈ 1,95 eV and a significant increase in the efficiency of the edge blue luminescence
band.
Keywords: zinc selenide, p-type conductivity, ionization energy, concentration, luminescence.
ceptor or donor) can be significantly improved
by the simultaneous introduction of an opposite
type of impurity [7, 8]. On the other hand, the
end result of this co-doping is difficult to predict,
since the complex process of defect formation
depends on many factors, i.e., the technology for
producing the base material and the ensemble of
point defects, the method and mode of introducing
compensating impurities, as well as their type and
combinations. etc. In this regard, all the methods
discussed above are far from simple, hard to pre-
dict theoretically, require complex and expensive
equipment, as well as extra annealing of defects
created due to the exposure to laser or ion fluxes.
With this in mind, doping these compounds
with isovalent impurities (IVIs) exhibiting a sig-
nificantly different behavior from that of typical
donor and acceptor impurities [4, 5, 9] may be
promising. One of the features of an IVI is that
it generates its intrinsic point defects (IPD) of a
certain type, not always creating their own local
levels in the forbidden zone of the semiconductor.
The type of IPD (donor or acceptor) determined
by the electronegativity factor XIVI and the atom
of a semiconductor compound replacing it, and the
concentration of the resulting IPD can be commen-
surate with the concentration of the introduced IVI
[6]. Using the results of [5, 6], we can conclude
that inequation XIVI < XZn must be fulfilled to
generate self-defective acceptor centers. This con-
dition is true for a number of elements from group
II of the periodic table (Be, Mg, Ca, Ba), whose
integration into the cationic (zinc) ZnSe sublattice
DOI: 10.15222/TKEA2019.3-4.31
Tekhnologiya i Konstruirovanie v Elektronnoi Apparature, 2019, No 3–4
32 ISSN 2225-5818
MATERIALS OF ELECTRONICS
2
stimulates the appearance of additional zinc vacan-
cies VZn and interstitial selenium Sei. Our choice
of calcium as an IVI is based on the fact that the
difference in the electronegativities of Ca and Zn
are fairly strong [5], and the solubility of calcium
salts in water is the highest compared to similar
salts of the other elements mentioned above [10].
Another feature of the IVI is an increase in the
edge radiation efficiency, whether the energy zone
structure is direct or indirect [11, 12]. This effect,
in particular, is observed experimentally in single-
crystal CdTe and ZnSe substrates doped with
group II elements with magnesium and calcium [7,
15]. Note that, regardless of the type of IVI used
(Mg and Ca) and the method of its introduction
(vapor phase or solution), the luminescence spectra
is dominated by the edge emission band at a doped
substrates temperature of 300 K. In our opinion,
the conclusions the authors of these works made
about the hole conductivity of the obtained layers
was not sufficiently substantiated.
Thus, in this study, we analyzed the electro-
physical properties of the ZnSe:Ca diffusion layers,
using the above-considered mechanisms for the
formation of acceptor centers and the determina-
tion of their main parameters.
Samples and research methods
The substrates were 4×4×1 mm plates cut from
a bulk ZnSe crystal grown from a stoichiometric
composition melt. In the room temperature range,
the substrates had a weak electronic conductivity
of σp ≈ 10–9 Ω–1∙cm–1. Before doping, the plates
underwent mechanical and chemical polishing in
solution CrO3:HCl = 2:3, which gave their surface
a mirror-like aspect. Doping was carried out by an
hour-long annealing of the substrates in a boiling
aqueous suspension of the Ca(NO3)2 salt. After
that, their surface layers changed the electron
conductivity to the hole one, which is confirmed
by the signs of thermoelectric power and by the
fact that the contact becomes rectifying. Then,
Ni was sprayed onto one of the large sides of the
plates in strips, which served as ohmic contacts
(OC) to the finial layer. A schematic representa-
tion of the substrates that have passed the stage
of annealing and OC deposition is shown in
Fig. 1 (see insert).
The linearity and symmetry of the current-
voltage characteristics (I—V) shown in Fig. 1 of
the Ni contacts confirms their resistivity and the
hole conductivity of the obtained layers (for clar-
ity, the values of the parameters of dependence 2
are multiplied by 103). At the same time, similar
contacts to n-ZnSe substrates have non-linear I—V
characteristics, which indicates the presence of
a potential barrier between nickel and zinc sel-
enide layers. Meanwhile, the above experimental
facts are not at all consistent with any of the
metal-semiconductor contact models (Schottky or
Bardeen) [16], which calls for additional research
beyond the scope of this work. Fortunately, this
does not prevent us from determining a number of
parameters of the obtained layers, in particular,
the ionization energy Ea and concentration Na of
electrically active acceptor centers. The former can
be found from the temperature dependence of the
specific conductivity.
Electronic conductivity σp or resistance ρp are
related to the concentration р0 and mobility μp of
equilibrium holes by a simple ratio [17]
σp = 1/ρp = eμpр0. (1)
Note that the dependency σp(Т) is actually
determined by the stronger dependence of the fac-
tors in (1) that vary with temperature according
to the law [17]
μp(Т) ~ Tm; р0 ~ T
3/2exp(–Ea/(nkT)). (2)
Here m changes from –3/2 to 3/2 depending
on the scattering mechanism, and n=1 or n=2 for
a strongly or slightly compensated semiconduc-
tor. Note also that in our case it is much easier to
Fig. 1. I—V characteristics of the ZnSe:Ca layer with
Ni contacts (1) and the substrate with In contacts (2)
obtained at 300 K
(insert presents a schematic drawing of the substrate after
annealing)
Ni
I∙10–6, А
l l0
ZnSe
d 1
2
(×103)
3
2
1
–1
–2
–3
–2 –1 1 2 U, В
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measure the resistance of the layer Rp, which then
allows you to easily calculate ρs (or σs) according
to the formula
ρp = 1/σp = Rps/l = Rpl0d/l, (3)
l, d — length and thickness of the diffusion layer;
l0 — width of the Ni contact (see the insert in Fig. 1).
The correctness of this approach is due to the
fact that the diffusion p-layer is isolated from the
substrate by an n-ZnSe i-layer with the lowest pos-
sible conductivity, which electrically unties them.
The ionization energy of electrically active centers
in the p-layer can be found using expressions (1)
and (2), assuming that σр(Т) is determined mainly
by the exponential factor, i. e., actually by p0(Т).
This is confirmed by the data in Fig. 2, which
shows that the experimental dependencies Rр(Т),
plotted in coordinates ln Rр – 10
3/ T, are straight
lines with the energy slope corresponding to the Ea
slope. The calculated values of the activation ener-
gies with regard to the weakly compensated p-layer
are given in Table and correlate with the depth
of the acceptor levels of alkali metal impurities
Ea ≈ 110—120 meV and singly charged zinc va-
cancies ZnV from Ea ≈ 150—200 meV [2, 17]. The
uncontrolled alkali metal impurities are likely to
be present in small quantities in the Ca(NO3)2 salt.
Using the parameters at the break points B1 and
B2 on the curve of Rр(Т) dependence at which the
Fermi level crosses the level of the correspond-
ing center, we can determine the concentration
of electrically active acceptor centers using the
formula [17]
Na = Nv exp(–Ea /(kТВ)). (4)
Effective density of state in the Nv valence
band is easily calculated by the formula
3/222 2 /pN m kT h . (5)
If we know that, for ZnSe, 00,6pm m [2],
we can calculate that Nv ≈ 8∙1019 cm–3 (for 300 К).
We can then find Na, given its dependence on T and
the corresponding Ea and TB values (see Table 1).
Due to the absence of a horizontal plot on the
graph of the dependence Rр(T) corresponding to
the “depletion” of the acceptor center, the free
holes concentration should be calculated by the
formula
0 1 1/ 2 exp / 2a ap N N E kT . (6)
Substituting the required values of Nv, Na1,
Ea1 and Т = 300 К into formula (6), we find that
p0 ≈ 8∙1017 cm–3, which, given the hole mobility
μр ≈ 30 cm
2/(V∙s) [2], leads to the conductivity
value σр ≈ 4 Ω–1∙cm–1. The diffusion layer thickness
is easy to find by substituting the experimental
and calculated parameters l, l0, Rp and σр into
expression (3). For this sample, the diffusion layer
thickness was determined to be approximately
0.15 μm.
In conclusion, we note that a sufficiently high
hole conductivity of the obtained layers cannot
be due to the new chemical compound formed as
a result of treatment in the Ca(NO3)2 aqueous
suspension. This is confirmed by a number of ex-
perimental facts. Firstly, the differential reflection
spectra of the base and doped ZnSe substrates are
identical, which indicates that their energy band
structures are the same [15]. Secondly, there is a B
band in the photoluminescence spectra of ZnSe:Ca
layers, the shape and energy position of which
are similar to the edge emission band of the base
Fig. 2. Temperature dependence of the ZnSe:Ca
diffusion layer resistance
B1
Rp,Ω
105
104
2.6 2.8 3.0 3.2 3.4 103/Т, К–1
B2
Ea1
Ea2
The main parameters of p-ZnSe:Ca layers
Parameter
Ea1,
meV
Ea2,
meV
ТВ1,
К
ТВ2,
К
Na1,
cm–3
Na2,
cm–3
p0,
cm–3
d,
μm
Value 110 200 320 380 1,6∙1018 3∙1017 8∙1017 0,15
Tekhnologiya i Konstruirovanie v Elektronnoi Apparature, 2019, No 3–4
34 ISSN 2225-5818
MATERIALS OF ELECTRONICS
4
substrates (Fig. 3, for clarity, the values of the
parameters of dependence 2 are multiplied by 0.2).
Of particular practical interest is the fact that,
in doped samples, the B-band is dominant, and
its efficiency at 300 K is almost an order of
magnitude greater than it is in base substrates
(see Fig. 3). Therefore, we can assume that the
observed transformation of the emission spectra is
associated with the rearrangement of an ensemble
of point defects in ZnSe, caused by the introduc-
tion of Ca impurity. We also draw attention to
the fact that the exciting radiation of the N2-laser
(λm ≈ 0,337 μm) penetrates to a depth of less than
0.1 μm, as a result of which it does not excite
the luminescence in the base substrate and the
observed emission spectrum is actually determined
by the ZnSe:Ca layer diffusion (curve 2 in Fig. 3).
Conclusion
Thus, the research results convincingly indicate
the possibility of creating p-type surface layers on
n-ZnSe substrates by annealing them in a boiling
aqueous suspension of Ca(NO3)2 salt. In this case,
the conductivity is controlled by acceptor centers
with activation energy values of 0.11 eV and
0.2 eV and estimated concentration of 1018 and
3∙1017 cm–3, respectively. The presence of an effec-
tive edge emission band at 300 K in the lumines-
cence spectra of ZnSe:Ca layers is also practically
important. Further research, in our opinion, should
be focused on studying the mechanisms of defect
formation and luminescence, as well as directly
determining the thickness of diffusion ZnSe:Ca
layers and holes in them.
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Received 09.04 2019
Fig. 3. Luminescence spectra of base (1) and Ca-doped (2)
n-ZnSe substrates obtained at 300 K
R
Nω, a. u.
1.0
0.5
0
1.6 1.8 2.0 2.2 2.4 2.6 ћω, eV
B
1
2
(×0.2)
Tekhnologiya i Konstruirovanie v Elektronnoi Apparature, 2019, No 3–4
35ISSN 2225-5818
MATERIALS OF ELECTRONICS
5
Д. ф. -м. н. В. П. МАХНИЙ, к. ф. -м. н. М. М. БЕРЕЗОВСКИЙ,
к. ф. -м. н. О. В. КИНЗЕРСКАЯ, к. ф. -м. н. В. В. МЕЛЬНИК
Украина, Черновицкий национальный университет
имени Юрия Федьковича
E-mail: oksanakinzerska@gmail.com, vpmakhniy@gmail.com
ПОВЕРХНОСТНЫЕ СЛОИ ZnSe:Ca С ДЫРОЧНОЙ ПРОВОДИМОСТЬЮ
Исследовано влияние обработки подложек n-ZnSe в кипящей водной суспензии соли Ca(NO3)2 на их элек-
трические и люминесцентные свойства. Базовые подложки вырезались из объемных беспримесных кри-
сталлов селенида цинка, выращенных методом Бриджмена из расплава стехиометрического состава.
Установлено, что обработка приводит к появлению дырочной проводимости поверхностных слоев под-
ложек, величина которой при 300 К составляет σp ≈ 4 Ом–1∙см–1. Значения энергии ионизации электри-
чески активных акцепторных центров, найденные из температурной зависимости сопротивления Rр ле-
гированного кальцием слоя селенида цинка, равны Ea1 ≈ 0,11 эВ и Ea2 ≈ 0,2 эВ. Значения их концентра-
ций, рассчитанные с учетом характерных точек излома на зависимости Rр(T), составляют для соот-
ветствующих центров Na1 ≈ 1,6∙1018 см–3 и Na2 ≈ 3∙1017 см–3. Оценочная концентрация свободных ды-
рок в полученных слоях при 300 К равна р0 ≈ 8∙1017 см–3. Установлено, что легирование подложек каль-
цием вызывает практически полное «гашение» низкоэнергетической оранжевой полосы излучения с мак-
симумом вблизи ћωmax ≈ 1,95 эВ и значительное увеличение эффективности краевой голубой полосы
люминесценции.
Ключевые слова: селенид цинка, дырочная проводимость, энергия ионизации, концентрация, люминесценция.
DOI: 10.15222/TKEA2019.3-4.31
УДК 537.32
Д. ф.-м. н. В. П. МАХНІЙ, к. ф.-м. н. М. М. БЕРЕЗОВСЬКИЙ,
к. ф.-м. н. О. В. КІНЗЕРСЬКА, к. ф.-м. н. В. В. МЕЛЬНИК
Україна, Чернівецький національний університет імені Юрія Федьковича
E-mail: oksanakinzerska@gmail.com, vpmakhniy@gmail.com
ПОВЕРХНЕВІ ШАРИ ZnSe:Ca З ДІРКОВОЮ ПРОВІДНІСТЮ
Досліджено вплив обробки підкладинок n-ZnSe в киплячій водній суспензії солі Ca(NO3)2 на їхні електричні
та люмінесцентні властивості. Базові підкладинки вирізались з об’ємних бездомішкових кристалів
селеніду цинку, вирощених методом Бріджмена із розплаву стехіометричного складу. Встановлено, що
обробка призводить до появи діркової провідності поверхневих шарів підкладинок, величина якої за
300 К складає σp ≈ 4 Ом–1∙см–1. Значення енергії іонізації електрично активних акцепторних центрів,
знайдені з температурної залежності опору Rр легованого кальцієм шару селеніду цинку, дорівнюють
Ea1 ≈ 0,11 еВ та Ea2 ≈ 0,2 еВ. Значення їхніх концентрацій, розраховані з врахуванням характер-
них точок зламу на графіку залежності Rр(T), складають для відповідних центрів Na1 ≈ 1,6∙1018 см–3
та Na2 ≈ 3∙1017 см–3. Оціночна концентрація вільних дірок в отриманих шарах за 300 К дорівнює
р0 ≈ 8•1017 см–3. Встановлено, що легування подкладинок кальцієм викликає практично повне «гасіння»
низькоенергетичної помаранчевої смуги випромінювання з максимумом поблизу ћωmax ≈ 1,95 еВ і значне
збільшення ефективності крайової блакитної смуги люмінесценції.
Ключові слова: селенід цинку, діркова провідність, енергія іонізації, концентрація, люмінесценція.
Опис статті для цитувания:
Makhniy V. P., Berezovskiy M. M., Kinzerska O. V.,
Melnyk V. V. Surface ZnSe:Ca layers with hole conductivity.
Техно логия и конструи рование в элек трон ной аппаратуре,
2019, № 3-4, с. 31—35. http://dx.doi.org/10.15222/
TKEA2019.3-4.31
Cite the article as:
Makhniy V. P., Berezovskiy M. M., Kinzerska O. V.,
Melnyk V. V. Surface ZnSe:Ca layers with hole conductivity.
Tekhnologiya i Konstruirovanie v Elektronnoi Apparature,
2019, no. 3-4, pp. 31–35. http://dx.doi.org/10.15222/
TKEA2019.3-4.31
DOI: 10.15222/TKEA2019.3-4.31
УДК 537.32
|
| id | nasplib_isofts_kiev_ua-123456789-167876 |
| institution | Digital Library of Periodicals of National Academy of Sciences of Ukraine |
| issn | 2225-5818 |
| language | English |
| last_indexed | 2025-12-07T17:07:56Z |
| publishDate | 2019 |
| publisher | Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України |
| record_format | dspace |
| spelling | Makhniy, V.P. Berezovskiy, M.M. Kinzerska, O.V. Melnyk, V.V. 2020-04-12T15:58:39Z 2020-04-12T15:58:39Z 2019 Surface ZnSe:Ca layers with hole conductivity / V.P. Makhniy, M.M. Berezovskiy, O.V. Kinzerska, V.V. Melnyk // Технология и конструирование в электронной аппаратуре. — 2019. — № 3-4. — С. 31-35. — Бібліогр.: 17 назв. — англ. 2225-5818 DOI: 10.15222/TKEA2019.3-4.31 https://nasplib.isofts.kiev.ua/handle/123456789/167876 621.315.529 The authors investigate the effect of treating n-ZnSe substrates with boiling aqueous Ca(NO₃)₂ suspension on their electrical and luminescent properties. Base substrates were cut from bulk pure zinc selenide crystals grown from a stoichiometric melt by the Bridgman method. It was found that the Ca-doping of the substrates causes an almost complete “quenching” of the low-energy orange emission band with a maximum near hωmax ≈ 1,95 eV and a significant increase in the efficiency of the edge blue luminescence band. Исследовано влияние обработки подложек n-ZnSe в кипящей водной суспензии соли Ca(NO₃)₂ на их элек-трические и люминесцентные свойства. Досліджено вплив обробки підкладинок n-ZnSe в киплячій водній суспензії солі Ca(NO₃)₂ на їхні електричні та люмінесцентні властивості. en Інститут фізики напівпровідників імені В.Є. Лашкарьова НАН України Технология и конструирование в электронной аппаратуре Метрология. Стандартизация Surface ZnSe:Ca layers with hole conductivity Поверхностные слои ZnSe:Ca с дырочной проводимостью Поверхневі шари ZnSe:Ca з дірковою провідністю Article published earlier |
| spellingShingle | Surface ZnSe:Ca layers with hole conductivity Makhniy, V.P. Berezovskiy, M.M. Kinzerska, O.V. Melnyk, V.V. Метрология. Стандартизация |
| title | Surface ZnSe:Ca layers with hole conductivity |
| title_alt | Поверхностные слои ZnSe:Ca с дырочной проводимостью Поверхневі шари ZnSe:Ca з дірковою провідністю |
| title_full | Surface ZnSe:Ca layers with hole conductivity |
| title_fullStr | Surface ZnSe:Ca layers with hole conductivity |
| title_full_unstemmed | Surface ZnSe:Ca layers with hole conductivity |
| title_short | Surface ZnSe:Ca layers with hole conductivity |
| title_sort | surface znse:ca layers with hole conductivity |
| topic | Метрология. Стандартизация |
| topic_facet | Метрология. Стандартизация |
| url | https://nasplib.isofts.kiev.ua/handle/123456789/167876 |
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