Vbe of a diode-connected transistor is a fairly predictable and stable characteristic of a BJT. It is quite linear and yields a large signal (-2mV/K, approximately). It would probably require at least single point calibration in your application, since variability is of the order of +/-10°C without calibration. I expect you will use this because it is very, very simple (resistor + transistor -> ADC) and "good enough" for your application. Now, for general interest--
Better is difference in Vbe of two matched BJT devices at exactly the same temperature (i.e. on the same die) at two currents differing by a large factor such as 10:1. Or Vbe of a single device at two currents, switched fast enough that the temperature does not vary between measurements. For a device with low base spreading resistance such as an BC547 it is almost independent of individual device characteristics. Diode-connected transistors have an ideality factor close to one and varying little from that (perhaps 1.008 or so) This yields a smaller signal (order of 200uV/K) but more than 10x more accurate without calibration (proportional to absolute temperature) - typically better than +/-1°C.
Almost every characteristic of every component has some temperature dependence so one can't say that any given idea is unsuitable, however some are definitely better than others, and I would say the Vbe of a diode-connected transistor or delta-Vbe is very good. The two-current method is the same principle used to measure the die temperature in your computer CPU, for example, and the PTAT voltage is used in band-gap voltage references.
If r is the ratio between currents, the voltage difference is
\$\Delta V_{BE} = \frac{nkT}{q}
\ln(r)\$
where n is the ideality factor, k is Boltzman's constant, T is temperature (Kelvin) and q is the charge on an electron.
Note that, except for n (which is very close to 1.00 for a diode-connected transistor, and does not vary much with a given type of transistor), there are only fundamental constants in the equation plus the current ratio (which you control).
(there are a few other sources of error but that's a very good first approximation)
The key thing is that Is (saturation current) in the Ebers-Moll equation is eliminated. Is varies widely and is not constant with temperature.